Injecting impure CO_(2)for enhanced gas recovery(CO_(2)-EGR)offers a dual benefit by improving natural gas extraction while enabling CO_(2)sequestration.However,the interactions between CO_(2),N_(2),and CH_(4)under re...Injecting impure CO_(2)for enhanced gas recovery(CO_(2)-EGR)offers a dual benefit by improving natural gas extraction while enabling CO_(2)sequestration.However,the interactions between CO_(2),N_(2),and CH_(4)under reservoir conditions require further investigation.This study employs Grand Canonical Monte Carlo(GCMC)and Molecular Dynamics(MD)simulations to quantify the adsorption and diffusion behaviors of CO_(2),N_(2),and CH_(4)in quartz nanopores over a pressure range of 1-24 MPa under varying water saturations and gas compositions.The results indicate that:(1)CO_(2)exhibits the broadest energy distribution and the strongest adsorption stability,occupying about 20%-30%more adsorption sites than CH_(4)or N_(2)and showing the least sensitivity to water saturation,with only a 30%reduction at 50%saturation,compared to 60%for CH_(4),giving CO_(2)a clear competitive advantage.(2)The adsorption and desorption behaviors are strongly pressure dependent,as increasing pressure reduces the adsorption layer area and shifts gas distribution from adsorption dominated to free phase.Competitive adsorption analysis reveals that while CO_(2)dominates displacement at low pressures,mixtures that contain N_(2)achieve higher CH_(4)desorption efficiency above 13 MPa by mitigating diffusion resistance.(3)A higher N_(2)fraction improves CH_(4)diffusion coefficients,thereby facilitating gas mobility and ensuring superior recovery performance under high-pressure conditions.This study advances the fundamental knowledge of microscale gas behavior in tight sandstones and supports the feasibility of impure CO_(2)injection as a practical strategy for sustainable gas production.展开更多
Vitrimers belong to a class of polymeric materials capable of bond exchange reactions,showing great promise for environmental protection and sustainable development.However,studies on the coupling mechanism between th...Vitrimers belong to a class of polymeric materials capable of bond exchange reactions,showing great promise for environmental protection and sustainable development.However,studies on the coupling mechanism between the bond exchange kinetics and segmental dynamics near the glass transition temperature(T_(g))remain scarce.Herein,we employed molecular dynamics simulations to investigate the dynamic heterogeneity of the segment motion and bond exchange in vitrimers.The simulation results revealed that the bond exchange energy barrier exerts a much stronger influence on the bond exchange kinetics than on the segmental dynamics.At lower temperatures,slower segmental relaxation further constraind the bond exchange rate.Additionally,increasing the bond exchange energy barrier markedly enhanced the dynamic heterogeneity of segment motion.A close correlation was observed between heterogeneity and bond exchange.This study elucidated the coupling mechanism between bond exchange and segmental dynamics at the molecular scale,thereby providing a theoretical basis for designing vitrimer materials with tunable dynamic properties.展开更多
Shale gas in southern China is found to contain economically valuable helium(He),which is inconsistent with conventional perspective that hydrocarbon gases in shale would dilute He to sub-economic levels.The adsorptio...Shale gas in southern China is found to contain economically valuable helium(He),which is inconsistent with conventional perspective that hydrocarbon gases in shale would dilute He to sub-economic levels.The adsorption of gases in the nanopores of organic matter is considered a crucial factor influencing the shale gas composition.The adsorption behaviors of He,methane(CH_(4))and their mixtures in kerogen nanopores were performed by the Grand Canonical Monte Carlo simulation.The molecular simulations of pure He reveal that He can be adsorbed in shale and the adsorption capacity of He increases with the burial depth of shale.Before the hydrocarbon generation from kerogen,He has been continually generated in shale,the simulations further demonstrate that pure He can be partially preserved in shale as adsorbed gas phase.The simulations of competitive adsorption between CH_(4) and He show that the adsorption selectivity of CH_(4)/He is consistently higher than 1.0 under the simulated conditions.This indicates that the previously adsorbed He will be displaced by CH_(4) and subsequently concentrated in hydrocarbon gas as free gas phase during the process of hydrocarbon gas generation from kerogen.After the termination of hydrocarbon gas generation,He continues to be generated in shale and preferentially concentrated in free shale gas.Therefore,the concentration of He in shale gas will gradually increase with the generation time of He.In addition,our simulations indicate that high pressure and deep burial depth can enhance the adsorption of He in kerogen,suggesting that deeply buried organic-rich shale probably retains more adsorbed helium.Molecular simulations of He adsorption provide new insights into the accumulation process of He in shale gas and are of great significance for assessing helium resource potential in shale gas.展开更多
Direct viscosification of CO_(2) offers promising alternative for mobility control and reduction in residual brine saturation,thus to improve the CO_(2) trapping in saline aquifers.Hydrocarbon oligomers,recognized for...Direct viscosification of CO_(2) offers promising alternative for mobility control and reduction in residual brine saturation,thus to improve the CO_(2) trapping in saline aquifers.Hydrocarbon oligomers,recognized for their exceptional properties,are considered as one of the most promising viscosifiers in displacement of brine-saturated porous media.However,the molecular-level mechanisms governing the solubility and viscosification of hydrocarbon oligomers in scCO_(2) remain poorly understood.In this study,we employ coarse-grained molecular models to advance our understanding in the effects of molecular structure of hydrocarbon oligomers on their solubility in scCO_(2).The coarse-grained models of five hydrocarbon oligomers with different numbers of methyl-branch(n-C32,P1D-2,P1D-3,P1D-6 and squalane)are established to investigate their effects on solubilization in scCO_(2).We demonstrate that the number of methyl groups has a monotonic correlation with the solubility of hydrocarbon oligomers when the molecular weights of oligomers are comparable.The radial distribution function reveals nC32,P1D and squalane are uniformly dispersed with separation distances of approximately 1.0–2.0 nm.The interaction energy between hydrocarbon oligomers and CO_(2) shows that the number of methylbranch in hydrocarbon oligomers can directly influence their solubility in scCO_(2).Molecular simulation results demonstrate that the interaction distances between the methyl-branch and CO_(2) are smaller than those of other molecular fragments.There are approximately 20%more CO_(2) molecules interacting with methyl-branch than with other parts.This work sets the stage for our future molecular dynamics study in viscosification by hydrocarbon oligomers with different branching length and interfacial phenomena in multiphase systems.展开更多
Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents...Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents,a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking.We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane(FDEE)as single solvents.By employing quantum calculations,molecular dynamics simulations,and interpretable machine learning,we establish significant correlations between fluorination patterns and electrolyte properties.Higher fluorination levels enhance FDEE stability but decrease conductivity.The symmetry of fluorination sites is critical for stability and viscosity,while exerting minimal influence on ionic conductivity.FDEEs with highly symmetric fluorination sites exhibit favorable viscosity,stability,and overall electrolyte performance.Conductivity primarily depends on lithium-anion dissociation or association.These findings provide design principles for rational fluoroether electrolyte design,emphasizing the trade-offs between stability,viscosity,and conductivity.Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.展开更多
The strategic dispersion of carbon nanotubes(CNTs)within triblock copolymer matrix is key to fabricating nanocomposites with the desired electrical properties.This study investigated the self-assembly and electrical b...The strategic dispersion of carbon nanotubes(CNTs)within triblock copolymer matrix is key to fabricating nanocomposites with the desired electrical properties.This study investigated the self-assembly and electrical behavior of a polystyrene-polybutadiene-polystyrene(SBS)matrix with CNTs of different aspect ratios using hybrid particle-field molecular dynamics simulations.Structural factor analysis of the nanocomposites indicated that CNTs with higher aspect ratios promoted the transition of the SBS matrix from a bicontinuous to a lamellar phase.The resistor network algorithm method showed that the electrical conductivity of SBS and CNTs nanocomposites was influenced by the interplay between the CNTs aspect ratios,concentrations,and domain sizes of the triblock copolymer SBS.Our research sheds light on the relationship between CNTs dispersion and the electrical behavior of SBS/CNTs nanocomposites,guiding the engineering of materials to achieve desired electrical properties through the modulation of CNTs aspect ratios and tailored sizing of triblock copolymer domains.展开更多
The pre-wetting of aggregate surface is a means to improve the interface performance of SBS modified asphalt and aggregate.The effect of pre-wetting technology on the interaction between SBS modified asphalt and aggre...The pre-wetting of aggregate surface is a means to improve the interface performance of SBS modified asphalt and aggregate.The effect of pre-wetting technology on the interaction between SBS modified asphalt and aggregate was analyzed by molecular dynamics simulation.The diffusion coefficient and concentration distribution of SBS modified asphalt on aggregate surface are included.The simulation results show that the diffusion coefficient of the aggregate surface of SBS modified asphalt is increased by 47.6%and 70.5%respectively after 110#asphalt and 130#asphalt are pre-wetted.The concentration distribution of SBS modified asphalt on the aggregate surface after pre-wetting is more uniform.According to the results of interface energy calculation,the interface energy of SBS modified bitumen and aggregate can be increased by about 5%after pre-wetting.According to the results of molecular dynamics simulation,the pre-wetting technology can effectively improve the interface workability of SBS modified bitumen and aggregate,so as to improve the interface performance.展开更多
The emerging two-dimensional(2D)membranes offer a promising way to improve the water desalination performance of traditional membranes.MXene/graphene oxide(GO) composite membrane are known for their high separation pe...The emerging two-dimensional(2D)membranes offer a promising way to improve the water desalination performance of traditional membranes.MXene/graphene oxide(GO) composite membrane are known for their high separation performance and structural stability.In this study,molecular simulations are performed to investigate the desalination performance of the 2D MXene/GO membrane.The results reveal that the surface of the MXene nanosheet could induce the formation of ordered water structures,thereby accelerating the water transport in the 2D membrane.The higher rejection rate would be found in MXene/GO membrane with a larger GO oxidation degree owing to the sterichindrance effect induced by the functional groups on the GO surface.Overall,the MXene/GO(20) membrane with the interlayer spacing of 0.9 nm shows the highest water permeability(37.22×10^(-7)L·m^(-1)·h^(-1)·bar^(-1),1 bar=0.1 MPa)and a salt rejection of 100%.The results could provide theoretical insights for developing 2D membranes for water desalination.展开更多
Our researches are based on the fact that the systems composed of polyacrylamide and montmorillonite under a kind of shear state often appear in some important practical processes like drilling well etc. The viscosity...Our researches are based on the fact that the systems composed of polyacrylamide and montmorillonite under a kind of shear state often appear in some important practical processes like drilling well etc. The viscosity of polyacrylamide is usually the most important one among the characteristics to decide if the practical processes succeed or not. Therefore, we studied the effect of hydrated montmorillonite on the viscosities of polyacrylamide with temperature and shear rate varying under confined shear by molecular simulation method. Adopting the condition of confined shear in the research could make our simulations and the practical processes as similar as possible. First, the model of one polyacrylamide polymer chain with 20 monomers linearly linking surrounded by water molecules between two of montmorillonite layers was constructed. Then canonical ensemble （NVT） MD simulations were carried out for the built model at different temperatures and shear rates. From the gained simulation results, we calculated the polymer＇s structural property-radius of gyration, which was directly related to the viscosity property of polyacrylamide polymer. It was found that the viscosity of the polyacrylamide polymer between hydrated clay layers decreased with the temperature increasing from 298 to 343 K under the condition of confined shear. The variation trend of viscosity from simulation results was also confirmed by our experiments. Besides, the viscosity of the polyacrylamide between hydrated clay layers decreased with the shear rate increasing within the range of higher shear rates.展开更多
Grand canonical Monte Carlo and molecular dynamics simulation methods are used to simulate oxygen sorption and diffusion in amorphous poly（lactic acid） （PLA）. The simulated solubility coefficient of oxygen is clos...Grand canonical Monte Carlo and molecular dynamics simulation methods are used to simulate oxygen sorption and diffusion in amorphous poly（lactic acid） （PLA）. The simulated solubility coefficient of oxygen is close to experimental data obtained from the quartz crystal microbalance but much higher than those from the time-lag method. This discrepancy is explained by using the dual-mode sorption model. It is found that oxygen sorotion in PLA is predominantly Langmuir type controlled, i.e., through the process of filling holes. The time--lag method only takes into account oxygen molecules that participate the diffusion process whereas a large proportion of oxygen molecules trapped in the void have little chance to execute hopping due to the glassy nature of PLA at room temperature. The simulated diffusion coefficient of oxygen is reasonably close to the data obtained from the time-lag method. The solubility coefficient of oxygen decreases linearly with increasing relative humidity while its diffusion coefficient firstly decreases and then increases as a function of relative humidity.展开更多
In this reported study, the density functional theory(DFT) was used at the(U)B3LYP/6-311G(d,p) level to investigate the stabilization process of the nitrate ester plasticized polyether propellant(NEPE). Molecular simu...In this reported study, the density functional theory(DFT) was used at the(U)B3LYP/6-311G(d,p) level to investigate the stabilization process of the nitrate ester plasticized polyether propellant(NEPE). Molecular simulations were conducted of the reaction that generates NO_(2), the autocatalytic and aging reaction triggered by the NO_(2), and the nitrogen dioxide absorption reaction of the stabilizers during the propellent stabilization process. These simulations were derived using the transition-state theory(TST)and variational transition-state theory(VTST). The simulation results suggested that the stabilization of the NEPE propellant consisted of three stages. First, heat and NO_(2) were generated during the denitrification reaction of nitroglycerine(NG) and 1,2,4-butanetriol trinitrate(BTTN) in the NEPE propellant.Second, nitroso products were generated by the reactions of N-Methyl-4-nitroaniline(MNA) and 2-nitrodiphenylamine(2NDPA) with NO_(2). Third, the stabilizers were exhausted and the autocatalytic reaction of NG and BTTN and the aging reaction of polyethylene glycol(PEG) were triggered by the heat and NO_(2)generated in the first stage. By comparing the energy barriers of the various reactions, it was found that the NO_(2)generated from the denitrification reaction significantly reduced the reaction energy barrier to 105.56-126.32 kJ/mol, also increased the reaction rate constant, and decreased the thermal stability and energetic properties of the NEPE propellant. In addition, the NO_(2)also weakened the mechanical properties of the NEPE propellant by attacking the-CH2groups and the O atoms in the PEG molecular chain. The energy barriers of the reactions of MNA and 2NDPA with NO_(2)(94.61-133.61 k J/mol) were lower than those of the autocatalytic and decomposition reactions of NG, BTTN, and the aging reactions of PEG(160.30-279.46 kJ/mol). This indicated that, by eliminating NO_(2), the stabilizer in the NEPE propellant can effectively prevent NO_(2)from reacting with the NG, BTTN, and PEG in the NEPE propellant. Consequently, this would help maintain the energy and mechanical properties of the NEPE propellant, thereby improving its thermal stability.展开更多
In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature.Mixture comp...In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature.Mixture composed of CO2 and H2 was selected as the model system to separate.The results show that CO2 selectivity in catenated MOFs with multi-porous frameworks is much higher than their non-catenated counterparts.The simulations also show that the electrostatic interactions are very important for the selectivity,and the contributions of different electrostatic interactions are different,depending on pore size,pressure and mixture composition.In fact,changing the electrostatic interactions can even qualitatively change the adsorption behavior.A general conclusion is that the electrostatic interactions between adsorbate molecules and the framework atoms play a dominant role at low pressures,and these interactions in catenated MOFs have much more pronounced effects than those in their non-catenated counterparts,while the electrostatic interactions between adsorbate molecules become evident with increasing pressure,and eventually dominant.展开更多
Polymeric materials have a broad range of mechanical and physical properties.They have been widely used in material science,biomedical engineering,chemical engineering,and mechanical engineering.The introduction of ac...Polymeric materials have a broad range of mechanical and physical properties.They have been widely used in material science,biomedical engineering,chemical engineering,and mechanical engineering.The introduction of active elements into the soft matrix of polymers has enabled much more diversified functionalities of polymeric materials,such as self-healing,electroactive,magnetosensitive,pH-responsive,and many others.To further enable applications of these multifunctional polymers,a mechanistic modeling method is required and of great significance,as it can provide links between materials’micro/nano-structures and their macroscopic mechanical behaviors.Towards this goal,molecular simulation plays an important role in understanding the deformation and evolution of polymer networks under external loads and stimuli.These molecular insights provide physical guidance in the formulation of mechanistic-based continuum models for multifunctional polymers.In this perspective,we present a molecular simulation-guided and physics-informed modeling framework for polymeric materials.Firstly,the physical theory for polymer chains and their networks is briefly introduced.It serves as the foundation for mechanistic-models of polymers,linking their chemistry,physics,and mechanics together.Secondly,the deformation of the polymer network is used to derive the strain energy density functions.Thus,the corresponding continuum models can capture the intrinsic deformation mechanisms of polymer networks.We then highlight several representative examples across multiphysics coupling problems to describe in detail for this proposed framework.Last but not least,we discuss potential challenges and opportunities in the modeling of multifunctional polymers for future research directions.展开更多
We employed the previously developed micro porous activated carbon models of different pore sizes ranges of 9-11?,10-12?,and 13-16?that were constructed by molecular simulation method based on a random packing of plat...We employed the previously developed micro porous activated carbon models of different pore sizes ranges of 9-11?,10-12?,and 13-16?that were constructed by molecular simulation method based on a random packing of platelets of carbon sheets,functionalized with oxygen containing groups,to study the adsorption behavior of methane molecules.In studying methane adsorption behavior,we used Grand Canonical Monte Carlo and Molecular Dynamics methods at different temperatures of 273.15,298.15 and303.15 K.Adsorption isotherms,isosteric heats of adsorption,adsorption energy distributions and porosity changes of the models during adsorption process were analyzed and discussed.Furthermore,radial distribution Functions,relative distribution and diffusion coefficients of methane molecules in activated carbon models at different temperatures were studied.After the analysis,the main results indicated that large micro pores activated carbons were favorable for storing methane at lower temperatures and small micro pores were the most favorable for adsorbing methane molecules at higher temperatures.Interestingly,the developed model structures showed high capacities to store methane molecule at ambient temperatures and low pressure.展开更多
Molecular simulation plays an increasingly important role in studying the properties of complex fluid systems containing charges,such as ions,piezoelectric materials,ionic liquids,ionic surfactants,polyelectrolytes,zw...Molecular simulation plays an increasingly important role in studying the properties of complex fluid systems containing charges,such as ions,piezoelectric materials,ionic liquids,ionic surfactants,polyelectrolytes,zwitterionic materials,nucleic acids,proteins,biomembranes and etc.,where the electrostatic interactions are of special significance.Several methods have been available for treating the electrostatic interactions in explicit and implicit solvent models.Accurate and efficient treatment of such interactions has therefore always been one of the most challenging issues in classical molecular dynamics simulations due to their inhomogeneity and long-range characteristics.Currently,two major challenges remain in the application field of electrostatic interactions in molecular simulations;(i)improving the representation of electrostatic interactions while reducing the computational costs in molecular simulations;(ii)revealing the role of electrostatic interactions in regulating the specific properties of complex fluids.In this review,the calculation methods of electrostatic interactions,including basic principles,applicable conditions,advantages and disadvantages are summarized and compared.Subsequently,the specific role of electrostatic interactions in governing the properties and behaviors of different complex fluids is emphasized and explained.Finally,challenges and perspective on the computational study of charged systems are given.展开更多
Black cotton soil in East Africa is not a stable engineering material for highway and railroad projects. Its strong swelling potential when it absorbs water causes distresses in subgrade of highway and railroad, and t...Black cotton soil in East Africa is not a stable engineering material for highway and railroad projects. Its strong swelling potential when it absorbs water causes distresses in subgrade of highway and railroad, and thus leads to failures of the projects. This paper presents study on the swelling characteristics of black cotton soil in East Africa. Lab tests were conducted to obtain its basic engineering properties, and the results show that black cotton soil contains high amount of montmorillonite and exchangeable cations and is strong expansive soil. Molecular modelling was exploited to further investigate water absorption ability of montmorillonite. Three different molecular models of montmorillonite were constructed and used for simulations, among which Types I and II montmorillonite represent the expansive soil montmorillonite in China, and Types II and III montmorillonite represent black cotton soil montmorillonite in East Africa. The results showed that the interlayer cations of Type III montmorillonite possessed the strongest water absorption ability based on analysis of radial distribution function(RDF) of cations. Interlayer compensatory cations of Na+ enhance the hydration ability of the other major cations, thus resulting in the strong swelling potential of East-Africa black cotton soil.展开更多
The shale gas is an unconventional supplementary energy to traditional fossil energy,and is stored in layered rocks with low permeability and porosity,which leads to the difficulty for exploration of shale gas.Therefo...The shale gas is an unconventional supplementary energy to traditional fossil energy,and is stored in layered rocks with low permeability and porosity,which leads to the difficulty for exploration of shale gas.Therefore,using CO_(2) gas to displace shale gas has become an important topic.In this work,we use molecular simulations to study the displacement of shale gas by flue gas rather than CO_(2),in which flue gas is modeled as a binary mixture of CO_(2) and N_(2) and the shale model is represented by inorganic Illite and organic methylnaphthalene.CH_(4) is used as a shale gas model.Compared to the pure CO_(2),flue gas is easily available and the cost of displacement by flue gas would become lower.Results indicate that the pore size of shale is an important factor in the process of displacing shale gas and simultaneously sequestrating flue gas,while the flue gas N_(2)-CO_(2) ratio shows a small effect on the process of CH_(4) displacement,because the high partial pressure of flue gas is the main driving force for displacement of shale gas.Moreover,the geological condition also has a significant effect on the process of CH_(4) displacement by flue gas.Therefore,we suggest that the burial depth of 1 km is suitable operation condition for shale gas displacement.It is expected that this work provides a useful guidance for exploitation of shale gas and sequestration of greenhouse gas.展开更多
Molecular simulations are now an essential part of modern chemistry and physics,especially for the investigation of macromolecules.They have evolved into mature approaches that can be used effectively to understand th...Molecular simulations are now an essential part of modern chemistry and physics,especially for the investigation of macromolecules.They have evolved into mature approaches that can be used effectively to understand the structure-to-property relationships of diverse macromolecular systems.In this article,we provide a tutorial on molecular simulations,focusing on the technical and practical aspects.Several prominent and classical simulation methods and software are introduced.The applications of molecular simulations in various directions of macromolecular science are thenfeatured by representative systems,including self-assembly,crystallization,chemical reaction,and some typical non-equilibrium systems.This tutorial paper provides a useful overview of molecular simulations in the rapid progress of macromolecular science,and suggests guidance for researchers who start exploiting molecular simulations in their study.展开更多
The adsorption behavior of CO_2, CH_4 and their mixtures in bituminous coal was investigated in this study. First, a bituminous coal model was built through molecular dynamic(MD) simulations, and it was confirmed to b...The adsorption behavior of CO_2, CH_4 and their mixtures in bituminous coal was investigated in this study. First, a bituminous coal model was built through molecular dynamic(MD) simulations, and it was confirmed to be reasonable by comparing the simulated results with the experimental data. Grand Canonical Monte Carlo(GCMC)simulations were then carried out to investigate the single and binary component adsorption of CO_2 and CH_4with the built bituminous coal model. For the single component adsorption, the isosteric heat of CO_2 adsorption is greater than that of CH_4 adsorption. CO_2 also exhibits stronger electrostatic interactions with the heteroatom groups in the bituminous coal model compared with CH_4, which can account for the larger adsorption capacity of CO_2 in the bituminous coal model. In the case of binary adsorption of CO_2 and CH_4mixtures, CO_2 exhibits the preferential adsorption compared with CH_4 under the studied conditions. The adsorption selectivity of CO_2 exhibited obvious change with increasing pressure. At lower pressure, the adsorption selectivity of CO_2 shows a rapid decrease with increasing the temperature, whereas it becomes insensitive to temperature at higher pressure. Additionally, the adsorption selectivity of CO_2 decreases gradually with the increase of the bulk CO_2 mole fraction and the depth of CO_2 injection site.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.U23A2022)the National Natural Science Foundation of China(Grant No.52474047)+2 种基金the Natural Science Foundation of Chongqing(Grant No.CSTB2024NSCQ-MSX0951)the Natural Science Foundation of Sichuan Province(Grant No.2025ZNSFSC1357)the National Science and Technology Major Project(Grant No.2025ZD1404307).
文摘Injecting impure CO_(2)for enhanced gas recovery(CO_(2)-EGR)offers a dual benefit by improving natural gas extraction while enabling CO_(2)sequestration.However,the interactions between CO_(2),N_(2),and CH_(4)under reservoir conditions require further investigation.This study employs Grand Canonical Monte Carlo(GCMC)and Molecular Dynamics(MD)simulations to quantify the adsorption and diffusion behaviors of CO_(2),N_(2),and CH_(4)in quartz nanopores over a pressure range of 1-24 MPa under varying water saturations and gas compositions.The results indicate that:(1)CO_(2)exhibits the broadest energy distribution and the strongest adsorption stability,occupying about 20%-30%more adsorption sites than CH_(4)or N_(2)and showing the least sensitivity to water saturation,with only a 30%reduction at 50%saturation,compared to 60%for CH_(4),giving CO_(2)a clear competitive advantage.(2)The adsorption and desorption behaviors are strongly pressure dependent,as increasing pressure reduces the adsorption layer area and shifts gas distribution from adsorption dominated to free phase.Competitive adsorption analysis reveals that while CO_(2)dominates displacement at low pressures,mixtures that contain N_(2)achieve higher CH_(4)desorption efficiency above 13 MPa by mitigating diffusion resistance.(3)A higher N_(2)fraction improves CH_(4)diffusion coefficients,thereby facilitating gas mobility and ensuring superior recovery performance under high-pressure conditions.This study advances the fundamental knowledge of microscale gas behavior in tight sandstones and supports the feasibility of impure CO_(2)injection as a practical strategy for sustainable gas production.
基金financially supported by the National Natural Science Foundation of China(Nos.52173020 and 52573023)。
文摘Vitrimers belong to a class of polymeric materials capable of bond exchange reactions,showing great promise for environmental protection and sustainable development.However,studies on the coupling mechanism between the bond exchange kinetics and segmental dynamics near the glass transition temperature(T_(g))remain scarce.Herein,we employed molecular dynamics simulations to investigate the dynamic heterogeneity of the segment motion and bond exchange in vitrimers.The simulation results revealed that the bond exchange energy barrier exerts a much stronger influence on the bond exchange kinetics than on the segmental dynamics.At lower temperatures,slower segmental relaxation further constraind the bond exchange rate.Additionally,increasing the bond exchange energy barrier markedly enhanced the dynamic heterogeneity of segment motion.A close correlation was observed between heterogeneity and bond exchange.This study elucidated the coupling mechanism between bond exchange and segmental dynamics at the molecular scale,thereby providing a theoretical basis for designing vitrimer materials with tunable dynamic properties.
基金supported by the National Key Research and Development Program of China(Grant No.2021YFA0719000)the Science Foundation of China University of Petroleum,Beijing(No.2462025XKBH007)the Research Foundation of China University of Petroleum-Beijing at Karamay(No.XQZX20240019)。
文摘Shale gas in southern China is found to contain economically valuable helium(He),which is inconsistent with conventional perspective that hydrocarbon gases in shale would dilute He to sub-economic levels.The adsorption of gases in the nanopores of organic matter is considered a crucial factor influencing the shale gas composition.The adsorption behaviors of He,methane(CH_(4))and their mixtures in kerogen nanopores were performed by the Grand Canonical Monte Carlo simulation.The molecular simulations of pure He reveal that He can be adsorbed in shale and the adsorption capacity of He increases with the burial depth of shale.Before the hydrocarbon generation from kerogen,He has been continually generated in shale,the simulations further demonstrate that pure He can be partially preserved in shale as adsorbed gas phase.The simulations of competitive adsorption between CH_(4) and He show that the adsorption selectivity of CH_(4)/He is consistently higher than 1.0 under the simulated conditions.This indicates that the previously adsorbed He will be displaced by CH_(4) and subsequently concentrated in hydrocarbon gas as free gas phase during the process of hydrocarbon gas generation from kerogen.After the termination of hydrocarbon gas generation,He continues to be generated in shale and preferentially concentrated in free shale gas.Therefore,the concentration of He in shale gas will gradually increase with the generation time of He.In addition,our simulations indicate that high pressure and deep burial depth can enhance the adsorption of He in kerogen,suggesting that deeply buried organic-rich shale probably retains more adsorbed helium.Molecular simulations of He adsorption provide new insights into the accumulation process of He in shale gas and are of great significance for assessing helium resource potential in shale gas.
基金the financial support and funding provided by the National Natural Science Foundation of China(Youth Talent Program,Key Special Project,Grant No.52341401 and Distinguished Scholar Program with a Grant No.52425402)High-level Start-up Funding from Peking University Shenzhen Graduate School,Shenzhen Science and Technology Foundation(Grant No.JCYJ20230807120807016)+2 种基金High-level Startup Funding from China University of Petroleum-Beijing(Grant No.2462024YJRC033)the China Postdoctoral Science(CPS)Foundation(Certificate No.2024M750106)the Postdoctoral Fellowship Program of CPS(Grant No.GZC20240051)。
文摘Direct viscosification of CO_(2) offers promising alternative for mobility control and reduction in residual brine saturation,thus to improve the CO_(2) trapping in saline aquifers.Hydrocarbon oligomers,recognized for their exceptional properties,are considered as one of the most promising viscosifiers in displacement of brine-saturated porous media.However,the molecular-level mechanisms governing the solubility and viscosification of hydrocarbon oligomers in scCO_(2) remain poorly understood.In this study,we employ coarse-grained molecular models to advance our understanding in the effects of molecular structure of hydrocarbon oligomers on their solubility in scCO_(2).The coarse-grained models of five hydrocarbon oligomers with different numbers of methyl-branch(n-C32,P1D-2,P1D-3,P1D-6 and squalane)are established to investigate their effects on solubilization in scCO_(2).We demonstrate that the number of methyl groups has a monotonic correlation with the solubility of hydrocarbon oligomers when the molecular weights of oligomers are comparable.The radial distribution function reveals nC32,P1D and squalane are uniformly dispersed with separation distances of approximately 1.0–2.0 nm.The interaction energy between hydrocarbon oligomers and CO_(2) shows that the number of methylbranch in hydrocarbon oligomers can directly influence their solubility in scCO_(2).Molecular simulation results demonstrate that the interaction distances between the methyl-branch and CO_(2) are smaller than those of other molecular fragments.There are approximately 20%more CO_(2) molecules interacting with methyl-branch than with other parts.This work sets the stage for our future molecular dynamics study in viscosification by hydrocarbon oligomers with different branching length and interfacial phenomena in multiphase systems.
基金supported by the Major Research Plan of the National Natural Science Foundation of China(92372104)Guangdong Basic and Applied Basic Research Foundation(2022A1515110016)+3 种基金the Recruitment Program of Guangdong(2016ZT06C322)R&D Program of Guangzhou(2023A04J1364)Fundamental Research Funds for the Central Universities(2024ZYGXZR043)TCL Science and Technology Innovation Fund。
文摘Electrolyte engineering with fluoroethers as solvents offers promising potential for high-performance lithium metal batteries.Despite recent progresses achieved in designing and synthesizing novel fluoroether solvents,a systematic understanding of how fluorination patterns impact electrolyte performance is still lacking.We investigate the effects of fluorination patterns on properties of electrolytes using fluorinated 1,2-diethoxyethane(FDEE)as single solvents.By employing quantum calculations,molecular dynamics simulations,and interpretable machine learning,we establish significant correlations between fluorination patterns and electrolyte properties.Higher fluorination levels enhance FDEE stability but decrease conductivity.The symmetry of fluorination sites is critical for stability and viscosity,while exerting minimal influence on ionic conductivity.FDEEs with highly symmetric fluorination sites exhibit favorable viscosity,stability,and overall electrolyte performance.Conductivity primarily depends on lithium-anion dissociation or association.These findings provide design principles for rational fluoroether electrolyte design,emphasizing the trade-offs between stability,viscosity,and conductivity.Our work underscores the significance of considering fluorination patterns and molecular symmetry in the development of fluoroether-based electrolytes for advanced lithium batteries.
基金financially supported by the National Natural Science Foundation of China(Nos.52273019,62173065,22133002,22273031,and 12274056)Fundamental Research Funds for the Central Universities(No.04442024074)+2 种基金NationalKey R&D Program of China(No.2022YFB3707300)Beijing Natural Science Foundation(No.4242040)Scientific Research Funds Project of Liaoning Provincial Department of Education(No.LJKZ0034)。
文摘The strategic dispersion of carbon nanotubes(CNTs)within triblock copolymer matrix is key to fabricating nanocomposites with the desired electrical properties.This study investigated the self-assembly and electrical behavior of a polystyrene-polybutadiene-polystyrene(SBS)matrix with CNTs of different aspect ratios using hybrid particle-field molecular dynamics simulations.Structural factor analysis of the nanocomposites indicated that CNTs with higher aspect ratios promoted the transition of the SBS matrix from a bicontinuous to a lamellar phase.The resistor network algorithm method showed that the electrical conductivity of SBS and CNTs nanocomposites was influenced by the interplay between the CNTs aspect ratios,concentrations,and domain sizes of the triblock copolymer SBS.Our research sheds light on the relationship between CNTs dispersion and the electrical behavior of SBS/CNTs nanocomposites,guiding the engineering of materials to achieve desired electrical properties through the modulation of CNTs aspect ratios and tailored sizing of triblock copolymer domains.
基金Funded by the Research Funds of China University of Mining and Technology(No.102523215)。
文摘The pre-wetting of aggregate surface is a means to improve the interface performance of SBS modified asphalt and aggregate.The effect of pre-wetting technology on the interaction between SBS modified asphalt and aggregate was analyzed by molecular dynamics simulation.The diffusion coefficient and concentration distribution of SBS modified asphalt on aggregate surface are included.The simulation results show that the diffusion coefficient of the aggregate surface of SBS modified asphalt is increased by 47.6%and 70.5%respectively after 110#asphalt and 130#asphalt are pre-wetted.The concentration distribution of SBS modified asphalt on the aggregate surface after pre-wetting is more uniform.According to the results of interface energy calculation,the interface energy of SBS modified bitumen and aggregate can be increased by about 5%after pre-wetting.According to the results of molecular dynamics simulation,the pre-wetting technology can effectively improve the interface workability of SBS modified bitumen and aggregate,so as to improve the interface performance.
基金supported by the National Natural Science Foundation of China(22078251,21706197)the Open Project of Hubei Key Laboratory of Novel Reactor and Green Chemical Technology(NRG202407)+1 种基金the Ministry-of-Education,Key Laboratory for the Synthesis and Application of Organic Functional Molecules(KLSAOFM2511)the Graduate Innovative Fund of Wuhan Institute of Technology(CX2023024)。
文摘The emerging two-dimensional(2D)membranes offer a promising way to improve the water desalination performance of traditional membranes.MXene/graphene oxide(GO) composite membrane are known for their high separation performance and structural stability.In this study,molecular simulations are performed to investigate the desalination performance of the 2D MXene/GO membrane.The results reveal that the surface of the MXene nanosheet could induce the formation of ordered water structures,thereby accelerating the water transport in the 2D membrane.The higher rejection rate would be found in MXene/GO membrane with a larger GO oxidation degree owing to the sterichindrance effect induced by the functional groups on the GO surface.Overall,the MXene/GO(20) membrane with the interlayer spacing of 0.9 nm shows the highest water permeability(37.22×10^(-7)L·m^(-1)·h^(-1)·bar^(-1),1 bar=0.1 MPa)and a salt rejection of 100%.The results could provide theoretical insights for developing 2D membranes for water desalination.
基金Funded by the National Natural Science Foundation of China(No.30871988)the Jiangsu Provincial Science and Technology Project(No.BK2014147110)
文摘Our researches are based on the fact that the systems composed of polyacrylamide and montmorillonite under a kind of shear state often appear in some important practical processes like drilling well etc. The viscosity of polyacrylamide is usually the most important one among the characteristics to decide if the practical processes succeed or not. Therefore, we studied the effect of hydrated montmorillonite on the viscosities of polyacrylamide with temperature and shear rate varying under confined shear by molecular simulation method. Adopting the condition of confined shear in the research could make our simulations and the practical processes as similar as possible. First, the model of one polyacrylamide polymer chain with 20 monomers linearly linking surrounded by water molecules between two of montmorillonite layers was constructed. Then canonical ensemble （NVT） MD simulations were carried out for the built model at different temperatures and shear rates. From the gained simulation results, we calculated the polymer＇s structural property-radius of gyration, which was directly related to the viscosity property of polyacrylamide polymer. It was found that the viscosity of the polyacrylamide polymer between hydrated clay layers decreased with the temperature increasing from 298 to 343 K under the condition of confined shear. The variation trend of viscosity from simulation results was also confirmed by our experiments. Besides, the viscosity of the polyacrylamide between hydrated clay layers decreased with the shear rate increasing within the range of higher shear rates.
基金Supported by Program of New Century Excellent Talents in University （NCET-07-0313）, the National Natural Science Foun- dation of China （20706019, 20876052）, Guangdong Science Foundation （$2011010002078）.
文摘Grand canonical Monte Carlo and molecular dynamics simulation methods are used to simulate oxygen sorption and diffusion in amorphous poly（lactic acid） （PLA）. The simulated solubility coefficient of oxygen is close to experimental data obtained from the quartz crystal microbalance but much higher than those from the time-lag method. This discrepancy is explained by using the dual-mode sorption model. It is found that oxygen sorotion in PLA is predominantly Langmuir type controlled, i.e., through the process of filling holes. The time--lag method only takes into account oxygen molecules that participate the diffusion process whereas a large proportion of oxygen molecules trapped in the void have little chance to execute hopping due to the glassy nature of PLA at room temperature. The simulated diffusion coefficient of oxygen is reasonably close to the data obtained from the time-lag method. The solubility coefficient of oxygen decreases linearly with increasing relative humidity while its diffusion coefficient firstly decreases and then increases as a function of relative humidity.
基金the support provided by the School of Physics and Optoelectronic Engineering of Ludong University。
文摘In this reported study, the density functional theory(DFT) was used at the(U)B3LYP/6-311G(d,p) level to investigate the stabilization process of the nitrate ester plasticized polyether propellant(NEPE). Molecular simulations were conducted of the reaction that generates NO_(2), the autocatalytic and aging reaction triggered by the NO_(2), and the nitrogen dioxide absorption reaction of the stabilizers during the propellent stabilization process. These simulations were derived using the transition-state theory(TST)and variational transition-state theory(VTST). The simulation results suggested that the stabilization of the NEPE propellant consisted of three stages. First, heat and NO_(2) were generated during the denitrification reaction of nitroglycerine(NG) and 1,2,4-butanetriol trinitrate(BTTN) in the NEPE propellant.Second, nitroso products were generated by the reactions of N-Methyl-4-nitroaniline(MNA) and 2-nitrodiphenylamine(2NDPA) with NO_(2). Third, the stabilizers were exhausted and the autocatalytic reaction of NG and BTTN and the aging reaction of polyethylene glycol(PEG) were triggered by the heat and NO_(2)generated in the first stage. By comparing the energy barriers of the various reactions, it was found that the NO_(2)generated from the denitrification reaction significantly reduced the reaction energy barrier to 105.56-126.32 kJ/mol, also increased the reaction rate constant, and decreased the thermal stability and energetic properties of the NEPE propellant. In addition, the NO_(2)also weakened the mechanical properties of the NEPE propellant by attacking the-CH2groups and the O atoms in the PEG molecular chain. The energy barriers of the reactions of MNA and 2NDPA with NO_(2)(94.61-133.61 k J/mol) were lower than those of the autocatalytic and decomposition reactions of NG, BTTN, and the aging reactions of PEG(160.30-279.46 kJ/mol). This indicated that, by eliminating NO_(2), the stabilizer in the NEPE propellant can effectively prevent NO_(2)from reacting with the NG, BTTN, and PEG in the NEPE propellant. Consequently, this would help maintain the energy and mechanical properties of the NEPE propellant, thereby improving its thermal stability.
基金Supported by the National Natural Science Foundation of China （20725622, 20706002, and 20876006）, Beijing Nova Program （2008B15） and the Dutch STW/CW Separation Technology Program （700.56.655-DPC.6243）.
文摘In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature.Mixture composed of CO2 and H2 was selected as the model system to separate.The results show that CO2 selectivity in catenated MOFs with multi-porous frameworks is much higher than their non-catenated counterparts.The simulations also show that the electrostatic interactions are very important for the selectivity,and the contributions of different electrostatic interactions are different,depending on pore size,pressure and mixture composition.In fact,changing the electrostatic interactions can even qualitatively change the adsorption behavior.A general conclusion is that the electrostatic interactions between adsorbate molecules and the framework atoms play a dominant role at low pressures,and these interactions in catenated MOFs have much more pronounced effects than those in their non-catenated counterparts,while the electrostatic interactions between adsorbate molecules become evident with increasing pressure,and eventually dominant.
基金the support from the Interdisciplinary Multi-Investigator Materials Proposals(IMMP)program of the Institute of Materials Science at the University of Connecticutfunding support from the National Science Foundation(CMMI-1762661 and CMMI-1934829)the funding support from the National Science Foundation(CMMI-1762567 and CMMI-1943598).
文摘Polymeric materials have a broad range of mechanical and physical properties.They have been widely used in material science,biomedical engineering,chemical engineering,and mechanical engineering.The introduction of active elements into the soft matrix of polymers has enabled much more diversified functionalities of polymeric materials,such as self-healing,electroactive,magnetosensitive,pH-responsive,and many others.To further enable applications of these multifunctional polymers,a mechanistic modeling method is required and of great significance,as it can provide links between materials’micro/nano-structures and their macroscopic mechanical behaviors.Towards this goal,molecular simulation plays an important role in understanding the deformation and evolution of polymer networks under external loads and stimuli.These molecular insights provide physical guidance in the formulation of mechanistic-based continuum models for multifunctional polymers.In this perspective,we present a molecular simulation-guided and physics-informed modeling framework for polymeric materials.Firstly,the physical theory for polymer chains and their networks is briefly introduced.It serves as the foundation for mechanistic-models of polymers,linking their chemistry,physics,and mechanics together.Secondly,the deformation of the polymer network is used to derive the strain energy density functions.Thus,the corresponding continuum models can capture the intrinsic deformation mechanisms of polymer networks.We then highlight several representative examples across multiphysics coupling problems to describe in detail for this proposed framework.Last but not least,we discuss potential challenges and opportunities in the modeling of multifunctional polymers for future research directions.
基金Funded by Natural Science Foundation of Shandong Province(No.ZR201702150018)China Postdoctoral Science Foundation Funding Scheme(No.2018M632747)+1 种基金the Fundamental Research Funds for the Central Universities(Nos.18CX02143A,17CX05017)New Faculty Start-up Funding from China University of Petroleum(No.YJ20170019).
文摘We employed the previously developed micro porous activated carbon models of different pore sizes ranges of 9-11?,10-12?,and 13-16?that were constructed by molecular simulation method based on a random packing of platelets of carbon sheets,functionalized with oxygen containing groups,to study the adsorption behavior of methane molecules.In studying methane adsorption behavior,we used Grand Canonical Monte Carlo and Molecular Dynamics methods at different temperatures of 273.15,298.15 and303.15 K.Adsorption isotherms,isosteric heats of adsorption,adsorption energy distributions and porosity changes of the models during adsorption process were analyzed and discussed.Furthermore,radial distribution Functions,relative distribution and diffusion coefficients of methane molecules in activated carbon models at different temperatures were studied.After the analysis,the main results indicated that large micro pores activated carbons were favorable for storing methane at lower temperatures and small micro pores were the most favorable for adsorbing methane molecules at higher temperatures.Interestingly,the developed model structures showed high capacities to store methane molecule at ambient temperatures and low pressure.
基金supported by the National Natural Science Foundation of China(21776093,21376089,41976203,21506178,21908066)。
文摘Molecular simulation plays an increasingly important role in studying the properties of complex fluid systems containing charges,such as ions,piezoelectric materials,ionic liquids,ionic surfactants,polyelectrolytes,zwitterionic materials,nucleic acids,proteins,biomembranes and etc.,where the electrostatic interactions are of special significance.Several methods have been available for treating the electrostatic interactions in explicit and implicit solvent models.Accurate and efficient treatment of such interactions has therefore always been one of the most challenging issues in classical molecular dynamics simulations due to their inhomogeneity and long-range characteristics.Currently,two major challenges remain in the application field of electrostatic interactions in molecular simulations;(i)improving the representation of electrostatic interactions while reducing the computational costs in molecular simulations;(ii)revealing the role of electrostatic interactions in regulating the specific properties of complex fluids.In this review,the calculation methods of electrostatic interactions,including basic principles,applicable conditions,advantages and disadvantages are summarized and compared.Subsequently,the specific role of electrostatic interactions in governing the properties and behaviors of different complex fluids is emphasized and explained.Finally,challenges and perspective on the computational study of charged systems are given.
基金Project(51878164) supported by the National Natural Science Foundation of ChinaProjects(BK20180149, BK20161421) supported by the Natural Science Foundation of Jiangsu Province, ChinaProject(KFJ170106) supported by Changsha University of Science & Technology via Open Fund of National Engineering Laboratory of Highway Maintenance Technology, China。
文摘Black cotton soil in East Africa is not a stable engineering material for highway and railroad projects. Its strong swelling potential when it absorbs water causes distresses in subgrade of highway and railroad, and thus leads to failures of the projects. This paper presents study on the swelling characteristics of black cotton soil in East Africa. Lab tests were conducted to obtain its basic engineering properties, and the results show that black cotton soil contains high amount of montmorillonite and exchangeable cations and is strong expansive soil. Molecular modelling was exploited to further investigate water absorption ability of montmorillonite. Three different molecular models of montmorillonite were constructed and used for simulations, among which Types I and II montmorillonite represent the expansive soil montmorillonite in China, and Types II and III montmorillonite represent black cotton soil montmorillonite in East Africa. The results showed that the interlayer cations of Type III montmorillonite possessed the strongest water absorption ability based on analysis of radial distribution function(RDF) of cations. Interlayer compensatory cations of Na+ enhance the hydration ability of the other major cations, thus resulting in the strong swelling potential of East-Africa black cotton soil.
文摘The shale gas is an unconventional supplementary energy to traditional fossil energy,and is stored in layered rocks with low permeability and porosity,which leads to the difficulty for exploration of shale gas.Therefore,using CO_(2) gas to displace shale gas has become an important topic.In this work,we use molecular simulations to study the displacement of shale gas by flue gas rather than CO_(2),in which flue gas is modeled as a binary mixture of CO_(2) and N_(2) and the shale model is represented by inorganic Illite and organic methylnaphthalene.CH_(4) is used as a shale gas model.Compared to the pure CO_(2),flue gas is easily available and the cost of displacement by flue gas would become lower.Results indicate that the pore size of shale is an important factor in the process of displacing shale gas and simultaneously sequestrating flue gas,while the flue gas N_(2)-CO_(2) ratio shows a small effect on the process of CH_(4) displacement,because the high partial pressure of flue gas is the main driving force for displacement of shale gas.Moreover,the geological condition also has a significant effect on the process of CH_(4) displacement by flue gas.Therefore,we suggest that the burial depth of 1 km is suitable operation condition for shale gas displacement.It is expected that this work provides a useful guidance for exploitation of shale gas and sequestration of greenhouse gas.
基金financially supported by the National Natural Science Foundation of China(Nos.22025302 and 21873053).
文摘Molecular simulations are now an essential part of modern chemistry and physics,especially for the investigation of macromolecules.They have evolved into mature approaches that can be used effectively to understand the structure-to-property relationships of diverse macromolecular systems.In this article,we provide a tutorial on molecular simulations,focusing on the technical and practical aspects.Several prominent and classical simulation methods and software are introduced.The applications of molecular simulations in various directions of macromolecular science are thenfeatured by representative systems,including self-assembly,crystallization,chemical reaction,and some typical non-equilibrium systems.This tutorial paper provides a useful overview of molecular simulations in the rapid progress of macromolecular science,and suggests guidance for researchers who start exploiting molecular simulations in their study.
基金Supported by the CNPC Huabei Oilfield Science and Technology Development Project(HBYT-CYY-2014-JS-378,HBYT-CYY-2015-JS-47)
文摘The adsorption behavior of CO_2, CH_4 and their mixtures in bituminous coal was investigated in this study. First, a bituminous coal model was built through molecular dynamic(MD) simulations, and it was confirmed to be reasonable by comparing the simulated results with the experimental data. Grand Canonical Monte Carlo(GCMC)simulations were then carried out to investigate the single and binary component adsorption of CO_2 and CH_4with the built bituminous coal model. For the single component adsorption, the isosteric heat of CO_2 adsorption is greater than that of CH_4 adsorption. CO_2 also exhibits stronger electrostatic interactions with the heteroatom groups in the bituminous coal model compared with CH_4, which can account for the larger adsorption capacity of CO_2 in the bituminous coal model. In the case of binary adsorption of CO_2 and CH_4mixtures, CO_2 exhibits the preferential adsorption compared with CH_4 under the studied conditions. The adsorption selectivity of CO_2 exhibited obvious change with increasing pressure. At lower pressure, the adsorption selectivity of CO_2 shows a rapid decrease with increasing the temperature, whereas it becomes insensitive to temperature at higher pressure. Additionally, the adsorption selectivity of CO_2 decreases gradually with the increase of the bulk CO_2 mole fraction and the depth of CO_2 injection site.
