Grand Canonical Monte Carlo Method Research Articles

Generalization of Biasing Particle Insertion and Deletion for Grand Canonical Monte Carlo Simulation.

A general formulation of biasing particle insertion/deletion for the grand canonical Monte Carlo (GCMC) simulation is presented. The proposed formulation unifies the concepts of the conventional cavity- and configurational-type biasing techniques and modifies a cavity biasing method to strictly satisfy the detailed balance condition. Numerical examples of this modified cavity bias method are presented for Lennard-Jones fluid and hydrogen adsorption on a platinum surface. The results obtained using this method are compared with those obtained using various GCMC methods. Furthermore, a rigorous on-the-fly on-lattice GCMC simulation for surface adsorption is formulated and performed for comparison. The numerical examples clearly demonstrate the efficiency and accuracy of the proposed formulation.

Microscopic scale influence of functional groups on the displacement behavior of coalbed methane by hot humid flue gas: a molecular simulation study based on the dynamic injection process

Building upon the CO2-ECBM technology (CO2-Enhanced Coaled Methane Recovery Technology), hot flue gas injection for displacing coalbed methane has been proposed to improve methane recovery efficiency and reduce the costs associated with CO2 capture during the displacement process as well as flue gas desulfurization and denitrification at coal-fired power plants. To explore the microscopic mechanisms of displacement and the influence of functional groups, this study used Molecular Dynamics (MD) and Grand Canonical Monte Carlo (GCMC) methods with Materials Studio software to model slit pores grafted with various functional groups for gas adsorption simulations. The adsorption characteristics of eight key functional groups (-C=OCH₃, -COOH, -CH₂OH, Ar-OH, -OCH₃, -C6H6, -CH₃, -CH₂) for hot flue gas and methane were analyzed, focusing on adsorption strengths and underlying mechanisms. Simulations of the dynamic injection of hot flue gas were conducted, monitoring energy changes and methane density distribution to establish the relationship between adsorption strength and the difficulty of coalbed methane (CBM) displacement. The results indicate that in this simulation, the methane displacement efficiency using hot flue gas to displace coalbed methane exceeded 98%, demonstrating significantly better displacement performance compared to the use of pure carbon dioxide or nitrogen. Although both methane and hot flue gas show that greater interaction energy with pores makes displacement more difficult, the underlying causes differ. A comparison of the interaction energies between different functional groups and various gases reveals that oxygen-containing functional groups (-C=OCH3, -COOH, -CH2OH, Ar-OH, -OCH3) are unfavorable for the displacement of coalbed methane by wet hot flue gas, whereas aliphatic hydrocarbons (-CH3, -CH2) facilitate the displacement process.

Utilizing molecular simulation, ideal adsorbed solution theory and ensemble learning algorithms to investigate adsorption and separation of sulfides on amorphous nanoporous materials

Using grand canonical Monte Carlo method, we investigated the adsorption of pure H2S and SO2 gases on amorphous materials, and the separation of CH4-H2S and CO2-SO2 mixtures. At 303 K, the optimal adsorbent for both gases was found to be HCP-Colina-id016, with 16 mmol/g. For CH4-H2S mixture, despite aCarbon-Marks-id002 exhibiting the highest selectivity (approximately 80), the H2S adsorption was low (around 1 mmol/g), while Kerogen-Coasne-id013 demonstrated a high H2S adsorption of 12 mmol/g with a selectivity of 20. In the case of CO2-SO2, HCP-Colina-id018 exhibited a SO2 selectivity exceeding 30, with a high SO2 adsorption of 12 mmol/g. The Ideal Adsorbed Solution Theory underestimated the adsorption and selectivity of both mixtures, particularly evident in CO2-SO2. Molecular simulations revealed that, for the CO2-SO2 system, CO2 underwent condensation, resulting in a sudden drop in the SO2 adsorption isotherm. However, IAST accurately predicted this abrupt change. Based on the adsorption data obtained from molecular simulations, we compared the predictive performance of four ensemble learning algorithms, namely Random Forest (RF), Gradient Boosted Decision Trees (GBDT), Extreme Gradient Boosting (XGBoost), and CatBoost, for H2S and SO2 pure gases in amorphous porous materials. The rankings were observed to be XGBoost > GBDT > RF > CatBoost.

Study on the Adsorption Law of n-Pentane in Silica Slit Nanopores.

As the main components of shale, inorganic minerals are important carriers for oil and gas adsorption, whose pore structures and surface properties have significant effects on the fluid adsorption capacity. In this study, slit nanopores (SNPs) were constructed by silica. To investigate the microscopic adsorption law of n-pentane in silica, the grand canonical Monte Carlo (GCMC) method was used to simulate the adsorption behaviors of n-pentane in silica nanoparticles. The effects of different surface wettability, pore size, temperature, and pressure values on the adsorption behavior of pentane were discussed, revealing the micro adsorption mechanism of pentane in silica with different pore sizes and wettability and evaluating the degree of oil and gas utilization. The research results indicate that the adsorption capacity of pentane is greatly affected by the temperature under low-pressure conditions. With the increase of the pore size, the adsorption capacity of pentane increases linearly, and the number of adsorbed pentane molecules gradually decreases. The availability of oil and gas increases, and the oil and gas are more easily extracted. As the surface hydrophobicity of minerals increases, the van der Waals force between minerals and pentane also increases, leading to an increase in the number of adsorbed states of pentane. The stronger the hydrophilicity of the wall, the fewer the pentane molecules adsorbed on the surface, which would improve the efficiency of oil and gas extraction. This study provides potential for the development of novel surfactants based on adsorption selectivity.

Molecular simulation study on the adsorption and storage behavior of CO2 in different matrix components of shale

ABSTRACT This study investigates the adsorption and storage behaviour of CO2 in the different matrix components of shale based on a molecular simulation method. First, based on the Grand Canonical Monte Carlo (GCMC) method, we successfully established five pore models three fluid models to study the effects of temperature, pressure, pore diameter, water content, and CH4 on the adsorption of CO2. Then, based on the actual data from the shale of the Longmaxi Formation in Sichuan Basin, China, the storage capacity of CO2 in the shale is determined by calculating the density distribution of CO2 and the proportion of excess adsorbed gas. The results demonstrate that both high temperatures and water content are unfavourable for the adsorption of CO2 in the shale pores. The adsorption of CO2 increases with rising pressure while it decreases with increasing pore size. The magnitude and stability of CO2 adsorption in the pores of various matrix components is as follows: organic matter > montmorillonite > illite > kaolinite > quartz. Compared to the scenarios neglecting the adsorption of CO2, the storage capacity of CO2 decreases by 7.87%. The main finding of this study is expected to provide theoretical guidelines for CO2 adsorption storage in shale.

Adsorption and Diffusion Properties of Gas in Nanopores of Kerogen: Insights from Grand Canonical Monte Carlo and Molecular Dynamics Simulations

Investigating the adsorption and diffusion processes of shale gas within the nanopores of kerogen is essential for comprehending the presence of shale gas in organic matter of shale. In this study, an organic nanoporous structure was constructed based on the unit structure of Longmaxi shale kerogen. Grand canonical Monte Carlo and molecular dynamics simulation methods were employed to explore the adsorption and diffusion mechanisms of pure CH4, CO2, and N2, as well as their binary mixtures with varying mole fractions. The results revealed that the physical adsorption characteristics of CH4, CO2, and N2 gases on kerogen adhered to the Langmuir adsorption law. The quantity of adsorbed gas molecules increased with rising pressure but decreased with increasing temperature. The variation in the heat of adsorption was also analyzed. Under identical temperature and pressure conditions, the adsorption of CH4 increased with higher mole fractions of CH4, whereas it decreased with greater mole fractions of CO2 and N2. Notably, CO2 molecules exhibited a robust interaction with kerogen molecules compared to the adsorption properties of CH4 and N2. Furthermore, the self-diffusion coefficient of gas within kerogen nanopores gradually decreased with increasing pressure or decreasing temperature. The diffusion capacity of gas molecules followed the descending order N2 > CH4 > CO2 under the same pressure and temperature conditions.

Giant Effect of CO2 Injection on Multiphase Fluid Adsorption and Shale Gas Production: Evidence from Molecular Dynamics.

Carbon dioxide (CO2) injection in unconventional gas-bearing shale reservoirs is a promising method for enhancing methane recovery efficiency and mitigating greenhouse gas emissions. The majority of methane is adsorbed within the micropores and nanopores (≤50 nm) of shale, which possess extensive surface areas and abundant adsorption sites for the sequestration system. To comprehensively discover the underlying mechanism of enhanced gas recovery (EGR) through CO2 injection, molecular dynamics (MD) provides a promising way for establishing the shale models to address the multiphase, multicomponent fluid flow behaviors in shale nanopores. This study proposes an innovative method for building a more practical shale matrix model that approaches natural underground environments. The grand canonical Monte Carlo (GCMC) method elucidates gas adsorption and sequestration processes in shale gas reservoirs under various subsurface conditions. The findings reveal that previously overlooked pore slits have a significant impact on both gas adsorption and recovery efficiency. Based on the simulation comparisons of absolute and excess uptakes inside the kerogen matrix and the shale slits, it demonstrates that nanopores within the kerogen matrix dominate the gas adsorption while slits dominate the gas storage. Regarding multiphase, multicomponent fluid flow in shale nanopores, moisture negatively influences gas adsorption and carbon storage while promoting methane recovery efficiency by CO2 injection. Additionally, saline solution and ethane further impede gas adsorption while facilitating displacement. Overall, this work elucidates the substantial effect of CO2 injection on fluid transport in shale formations and advances the comprehensive understanding of microscopic gas flow and recovery mechanisms with atomic precision for low-carbon energy development.

Hydrogen storage in M(BDC)(TED)0.5 metal-organic framework: physical insights and capacities.

Finding renewable energy sources to replace fossil energy has been an essential demand in recent years. Hydrogen gas has been becoming a research hotspot for its clean and free-carbon energy. However, hydrogen storage technology is challenging for mobile and automotive applications. Metal-organic frameworks (MOFs) have emerged as one of the most advanced materials for hydrogen storage due to their exceptionally high surface area, ultra-large and tuneable pore size. Recently, computer simulations allowed the designing of new MOF structures with significant hydrogen storage capacity. However, no studies are available to elucidate the hydrogen storage in M(BDC)(TED)0.5, where M = metal, BDC = 1,4-benzene dicarboxylate, and TED = triethylenediamine. In this report, we used van der Waals-dispersion corrected density functional theory and grand canonical Monte Carlo methods to explore the electronic structure properties, adsorption energies, and gravimetric and volumetric hydrogen loadings in M(BDC)(TED)0.5 (M = Mg, V, Co, Ni, and Cu). Our results showed that the most favourable adsorption site of H2 in M(BDC)(TED)0.5 is the metal cluster-TED intersection region, in which Ni offers the strongest binding strength with the adsorption energy of -16.9 kJ mol-1. Besides, the H2@M(BDC)(TED)0.5 interaction is physisorption, which mainly stems from the contribution of the d orbitals of the metal atoms for M = Ni, V, Cu, and Co and the p orbitals of the O, C, N atoms for M = Mg interacting with the σ* state of the adsorbed hydrogen molecule. Noticeably, the alkaline-earth metal Mg strongly enhanced the specific surface area and pore size of the M(BDC)(TED)0.5 MOF, leading to an enormous increase in hydrogen storage with the highest absolute (excess) gravimetric and volumetric uptakes of 1.05 (0.36) wt% and 7.47 (2.59) g L-1 at 298 K and 7.42 (5.80) wt% and 52.77 (41.26) g L-1 at 77 K, respectively. The results are comparable to the other MOFs found in the literature.

Chemical reaction process and dynamic characteristics of urea pyrolysis products in inhibiting gas explosion

During the coal mining process, gas explosions pose significant hazards, causing casualties and property losses. In order to develop new types of inhibitors for gas explosions, this paper explores the reaction mechanisms of urea pyrolysis products NH3 and HNCO inhibiting gas explosions based on density functional theory (DFT), transition state theory, and grand canonical ensemble Monte Carlo method (GCMC). It analyzes the reaction processes and kinetic characteristics of urea pyrolysis products with key radicals and gas molecules involved in explosions from a microscopic dynamic perspective. The results show that urea pyrolysis products exhibit good inhibition effects on active radicals involved in explosion reactions·NH3 and HNCO show stronger van der Waals forces in electrostatic attraction towards O2 and *H, respectively, and faster rate advantages in reaction rate constants. The lower Gibbs free energy barrier indicates higher reaction activity of pyrolysis products, thereby diluting the concentration of key radicals involved in explosion reactions and effectively inhibiting explosion key elementary reactions (R32, R38, R53, R57, R156, and R170). This study provides new insights into the microscopic inhibition mechanism of urea pyrolysis products on gas explosions, offering a new approach for designing more targeted modified inhibitors, which helps reduce the hazards of gas explosions during coal mining and provides scientific support and technical guidance for safe coal mining production.

Molecular simulation of competitive adsorption of CO2/N2/O2 gas in bituminous coal

The main cause of coal spontaneous combustion is the oxidation and temperature rise of coal. Injecting composite inert gas for fire prevention and extinguishing is one of the important methods to prevent coal spontaneous combustion. A large number of studies have macroscopically investigated the fire prevention and extinguishing effects of CO2/N2 and their synergistic actions. However, there is currently a lack of research at the molecular level on the competitive adsorption mechanism between mixed inert gases (CO2, N2) and O2 molecules in coal. Therefore, this study conducted adsorption experiments using Qian Yingzi(QYZ) bituminous coal and compared them with the simulation data of the Wiser coal model to verify the reliability of the Wiser model. Subsequently, employing grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) methods, the competitive adsorption behavior of different proportions of binary mixed component gases (CO2/O2, CO2/N2, O2/N2) at a temperature of 303.15 K was investigated from five perspectives: adsorption capacity, adsorption selectivity coefficient, potential energy distribution, competitive adsorption heat, and interaction energy. The results indicate that among the competitive component gases, CO2 exhibits the strongest adsorption effect on the entire system, which is closely correlated with the distribution range of adsorption energy sites. The adsorption heat and adsorption amount of CO2 consistently exhibit a negative correlation, whereas the relationship between the adsorption heat of N2 and O2 and the adsorption amount shows a positive correlation. Their adsorption capacities depend on the pressure and the proportion of the two gases. Based on the isothermal adsorption curve of CO2/N2, it is recommended that the gas pressure during actual inert gas injection be less than 2.5 MPa. Under this pressure, the competitive adsorption effect is no longer significant, providing a certain theoretical basis for high-pressure injection. Moreover, the preliminary determination of the optimal injection ratio range is from 4:6–3:7. Furthermore, a systematic logical framework for selecting underground inert gas composition is proposed, and an underground mobile inert gas infusion process is adopted. The actual gas composition for infusion is determined based on cost factors in practical engineering. The research results can provide guidance for the selection of gas injection parameters for mixed inert gas fire prevention and extinguishing in goaf.

Investigation of the microscopic mechanism of H2O adsorption by low-rank coal slit pores through GCMC and MD simulations

This study investigates the influence of pore structure on H2O adsorption in low-rank coal (LRC) models at a molecular level, employing variously sized LRC slit-pore models·H2O adsorption behavior is analyzed across different pore sizes ranging from 0.001 to 100 kPa fugacity, by employing the Grand canonical Monte Carlo (GCMC) method and molecular dynamics (MD) simulations to explore saturated adsorption kinetics. The findings indicate a positive correlation between H2O adsorption levels and both fugacity and pore diameter. Furthermore, at constant pore diameter, the adsorption heat increases exponentially with increasing adsorption levels. Notably, H2O adsorption in LRC slit pores exhibits multilayer adsorption characteristics. First, adsorption occurs as monomolecular layers on the LRC surface, transitioning to secondary adsorption sites formed by previously adsorbed H2O molecules with increasing fugacity, ultimately saturating the pores. This adsorption process exhibits a correlation with a shift in potential energy distribution from high to low potential energy directions. Moreover, the ordering of H2O molecule arrangements between hydrogen atoms, oxygen atoms, and H2O molecules decreases with increasing pore diameters. Larger pore diameters correspond to increased H2O molecule diffusion, the stronger interaction between the LRC slit pores and H2O molecules but reduced interaction with individual H2O molecules. Overall, this study establishes a theoretical foundation for further studies on coal pore wetting and offer valuable insights for studies aimed at reducing dust and preventing gas outbursts.

Macromolecular insight into the adsorption and migration properties of CH4/CO2/N2 in bituminous coal matrix under uniaxial strain loading

Gas adsorption–migration in coal is of crucial importance for coalbed methane (CBM) recovery; however, the effect of coal deformation on it is not yet very clear, especially at the molecular level. In this study, the effects of uniaxial tension–compression strains on the CH4/CO2/N2 adsorption–migration characteristics in bituminous coal matrix were investigated by integrating the grand canonical Monte Carlo and molecular dynamics methods. The results show that the dual-mode equation fits the isothermal adsorption results, and the adsorption concentration and Langmuir volume are positively correlated with strain. Tension strain has a small effect on a thermodynamic factor but a large effect on Henry constant. In addition, the swelling resistance of coal matrix is positively correlated with tension strain which has a greater impact on the shear resistance of coal matrix containing CO2. The average mass density of the gas is linearly positively correlated with strain that has a large impact on N2 stability. More significantly, the self-diffusion coefficient (Ds) of CH4 is larger than that of CO2/N2, and the relationship between Fick diffusion coefficient and strain is roughly similar to that between Ds and strain. Also, the mass transfer of CO2 permeation is more significant compared to N2, especially for tension strain. These research results provide a basis for the optimization design of CBM recovery in deformed coal reservoirs.

Investigation of water adsorption characteristics of MgCl2 salt hydrates for thermal energy storage: Roles of hydrogen bond networks and hydration degrees

Thermochemical energy storage holds great promise in solar energy applications, and MgCl2 hydrate salt is considered a promising material for medium and low-temperature thermochemical energy storage. Understanding the adsorption behavior of water molecules in MgCl2 hydrate salts and uncovering the underlying mechanisms are crucial for designing efficient thermochemical energy storage systems. This paper investigated the water adsorption characteristics of MgCl2 hydrate salt utilizing the Grand Canonical Monte Carlo (GCMC) method and captured the adsorption isotherm and concentration distributions of water molecules in MgCl2 hydrate salts pores at various temperatures. The results demonstrate that at low temperatures, particularly when the pore size is small (D < 0.8 nm), the interconnected hydrogen bond network plays a crucial role in enhancing the water adsorption capacity of pure MgCl2. As the temperature increases, the influence of hydrogen bond networks diminishes, and their impact on the water adsorption capacity becomes negligible. Moreover, the hydration degrees of MgCl2 salt significantly influence their water adsorption capacity. MgCl2·6H2O exhibits the best water-uptake performance, followed by MgCl2·4H2O, while MgCl2·2H2O displays the worst water-uptake performance. These findings shed light on the adsorption behavior of water molecules in MgCl2 hydrate salt and offer valuable insights into the design and optimization of efficient thermochemical energy storage systems. Such knowledge is essential for advancing the utilization of thermochemical energy storage in solar energy applications.

Research on CO2/CH4/N2 competitive adsorption characteristics of anthracite coal from Shanxi Sihe coal mine.

This study aims to solve the problem of unsatisfactory development and utilization of coalbed methane and CO2 storage efficiency. It is focused on the adsorption behavior of CO2, CH4, and N2 in the macromolecular structure model of Shanxi Sihe coal mine anthracite, as well as the competitive adsorption behavior of CO2/CH4 and CH4/N2 binary gas mixtures with different ratios. Experimental analysis such as elemental analysis, solid 13C nuclear magnetic resonance (13C NMR), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis were used to construct the Shanxi Sihe coal mine model of the macromolecular structure of anthracite coal. The Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulation methods were used to study the adsorption capacity and heat characteristics of CO2, CH4, and N2 at different temperatures using a molecular model of anthracite coal from Shanxi Sihe coal mine, as well as the competitive adsorption characteristics of CO2/CH4 and CH4/N2 binary mixtures. The mechanism of the influence of temperature and gas properties on the adsorption capacity and heat of adsorption was revealed from a microscopic perspective. The results indicated that the aromatic carbon content of anthracite in the Sihe coal mine, Shanxi is 81.19%, and the ratio Xbp of aromatic bridgehead carbon to surrounding carbon is 0.489. The aromatic structure is mainly composed of pyrene and anthracene. The molecular formula of the macromolecular structure model of anthracite in Shanxi Sihe coal mine is C233H157O13N2. The adsorption capacity and equivalent adsorption heat of the macromolecular model for adsorbing single-component gas CO2/CH4/N2 decrease with the increase in temperature. The temperature has the greatest impact on CO2 adsorption capacity and adsorption heat, followed by CH4 and N2. Under the competitive adsorption conditions of CO2/CH4 and CH4/N2 binary mixtures, the higher the partial pressure of a single-component gas in the mixture, the greater the adsorption capacity of the gas. The difference in the adsorption heat of CH4 and N2 is smaller than that of CH4 and CO2. The conclusions obtained from the study can provide technical and theoretical support for formulating reasonable drainage methods for coalbed methane wells.

A detailed molecular dynamics simulation and experimental investigation of CO2 adsorption on graphene oxide-polyaniline nanocomposite

The study investigated the sorption and diffusion of carbon dioxide on Graphene oxide-polyaniline (GO-PANI) using volumetric method and molecular dynamics simulations. The experimental results showed that GO-PANI was more effective at adsorbing CO2 than either of the individual materials alone. Simulations supported this trend in CO2 adsorption and provided additional insights into the structural information of the adsorbents and the dynamics of CO2 molecules. The Langmuir adsorption model was employed to fit sorption isotherms computed using Grand Canonical Monte Carlo (GCMC) method. The GO-PANI nanocomposite compound exhibited a superior adsorption rate compared to pure structures. The isosteric heat for CO2 adsorption was 27.59 kJ/mol. The interaction energy of single molecules of CO2 on GO-PANI surface was −38.075 kcal/mol. Diffusion coefficient value for CO2 was 41.2 × 10 −9 m2/s, lower than that of the pure polymer. FT-IR, FE-SEM, and BET techniques were used to analyze synthesized GO-PANI structure. The highest CO2 adsorption was observed at a temperature of 283 K. Isosteric heat adsorption decreased with uniform surface charge. This research provides critical microscopic information on gas adsorption in polymer nanocomposites and demonstrates the effectiveness of GO-PANI as an efficient adsorbent for carbon dioxide, which could be useful in various industrial applications.

Transport property of hydrogen sulfide in amorphous polyethylene using grand canonical Monte Carlo and molecular dynamics simulations

H2S corrosion poses a significant hurdle to safely transporting sulfur-containing natural gas through metal gathering pipes. Reinforced thermoplastic composite pipes have emerged as a solution, using the polyethylene inner lining layer that resists H2S corrosion. However, the permeation of H2S in the polyethylene may lead to the failure of reinforced thermoplastic composite pipes, resulting in natural gas leakage and environmental pollution. Therefore, it is crucial to investigate the gas transport properties of H2S in polyethylene materials to ensure the reliable functioning of gathering pipes. In this study, the dissolution behavior of H2S for pure H2S and H2S/CH4 mixture in amorphous PE is investigated using the grand canonical Monte Carlo method in conjunction with the NPT, with consideration given to the swelling effect. In addition, the diffusion characteristic is explored through the NVT on the amorphous PE adsorbing H2S. Subsequently, the permeability coefficient is calculated based on the obtained data. The findings reveal that with as the temperature increases, the solubility coefficient decreases, while both the diffusion and permeability coefficients increase. With increasing pressure, both the diffusion and permeability coefficients increase. Additionally, the above three coefficients all increase with increasing H2S mole fraction. The relationships between solubility, diffusion, and permeability coefficients & temperature all conform to the Arrhenius law. Finally, the diffusion mechanism of H2S in amorphous PE is revealed at the microscopic level as the “jumping” mechanism by tracking the diffusion pathway of H2S molecule.

Competitive sorption of CO2/CH4 and CO2 capture on modified silica surfaces: A molecular simulation

The effect of functionalization of modified silica (FMS) surfaces on the adsorption behaviors for CH4, CO2 and the mixture have been studied by combining a grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) methods. The isotherms, gas distribution, sorption sites, isosteric heat, interaction energy and adsorption selectivity for CO2/CH4 mixture are computed and discussed. And the effects of pressure and temperature on adsorption behavior are also studied. The adsorption capacity (C) of surface with various functional groups for CH4 is as follows: C(SiO2-COOH) > C(SiO2-SH) > C(SiO2-OH) > C(SiO2-CH3) > C(SiO2-NH2) > C(SiO2-H) and for CO2 is as follows: C(SiO2-COOH) > C(SiO2-SH) > C(SiO2-NH2) > C(SiO2-OH) > C(SiO2-CH3) > C(SiO2-H). Increasing temperature is not advantageous for gas adsorption on all FMS surfaces. The CO2/CH4 selectivity (S) for FMS surfaces decrease in the following order of S(SiO2-COOH) > S(SiO2-NH2) > S(SiO2-OH) > S(SiO2-SH) > S(SiO2-CH3) > S(SiO2-H). As the pressure increase, the CO2/CH4 selectivity decrease early and then flatten out to a constant value. The isosteric heat of adsorption (Qst) for gas adsorbed on each FMS surface are also calculated, the value of isosteric heat for CO2 is much higher than that for CH4 due to the stronger interaction between CO2 molecules and functional groups of FMS surface. The result of the smallest self-diffusion coefficients of gas in SiO2-COOH slit pores is consistent with the adsorption capacity in the slit pore with corresponding functional group. The electronegative atoms in the functional group act as basic adsorption sites for gas adsorbate molecules, which generates a larger electrostatic contribution on the selectivity of CO2 over CH4.

Adsorption behaviors for clathrate hydrates of CO2 with mixed gases

Here, the preference and adsorption capacities of guest molecules in the sI and sII hydrate of water cages when CO2 + H2S, CO2 + SO2 and CO2 + N2O gas mixture form hydrates are simulated by using grand canonical Monte Carlo and molecular dynamics hybrid simulations method. The results indicate that SO2 prefers to occupy large cages, H2S prefers small cages for CO2 + H2S and CO2 + SO2 and N2O exhibits little preference between small or large or cages of CO2 + N2O sI hydrates, respectively. The abundance ratio shows hydrate can effectively achieve the separation of flue gases. Moreover, the thermodynamics calculation results show that the impurity gases H2S, SO2 and N2O favors the formation of CO2 hydrate. The stability CO2 + H2S, CO2 + SO2 and CO2 + N2O sI hydrates is higher compared to the stability of sII hydrates. The phase equilibrium analysis provides clear evidence that enclathration of H2S and SO2 molecules into the water cages of the hydrate structure plays a crucial role in stabilizing the hydrate lattices. The findings of this study suggest that removal of certain flue gas impurities is not required during the replacement of CH4 in hydrate form with the CO2 gas. The current investigation provides theoretical background for executing replacement of CH4 in hydrate form with the CO2 gas.

Adsorption performance of the functional COFs for removal of bisphenol A: Molecular dynamic simulations

The inherent structural features of the covalent organic frameworks (COFs) play a crucial role in determining their adsorption performances for bisphenol A (BPA). The computational methods were advantageous in unraveling intrinsic molecular properties about their performances. Herein, some COFs with different functional groups (–COOH, –NH2, –NO2 and –CF3) were designed to demonstrate the efficacy of the functional COFs for adsorbed BPA in gas phase and aqueous solution. The density functional theory (DFT) and Grand Canonical Monte Carlo (GCMC) methods were used to analyze the interaction energy between COFs and BPA, structure properties, and adsorption performances etc.. The results indicated that the addition of strong electronegative functional groups in COFs increased these COFs’ isosteric heat of adsorption (Qst) (TpBD-(COOH)2 > TpBD-(CF3)2 > TpBD-(NH2)2 > TpBD-(NO2)2 > TpBD) for gas phase BPA, but their introduction also reduced the pore size of COFs (TpBD > TpBD-(COOH)2 > TpBD-(NH2)2 > TpBD-(CF3)2 > TpBD-(NO2)2). However, these functional COFs demonstrated the stronger the adsorption capacity for gas phase BPA (At 298 K and 1 bar, the BPA uptake of TpBD-(COOH)2, TpBD-(NH2)2, TpBD, TpBD-(NO2)2 and TpBD-(CF3)2 was 242.52, 232.43, 219.31, 206.64 and 197.73 mg/g, respectively.). The amount of BPA adsorbed by functional COFs was the result of the synergistic effect of the electronegativity of functional groups and the pore size. Molecular dynamic (MD) simulation performed the same phenomenon for BPA in aqueous solution. In addition, the higher temperature will decrease the adsorption amount of BPA by COF, but increase its desorption ability.

Adsorption behavior of H2 in quartz silt-pores at high temperature and pressure

To understand the storage and transport of H2 in the Earth’s interior, the adsorption behaviors of H2 in the slit-like pore of quartz under different conditions were calculated by the grand canonical Monte Carlo method. The Poisson distributions of interaction energy show unimodal, indicating that the adsorption behavior is mainly affected by van der Waals interaction between molecular H2 and quartz, the adsorption potential energy increases, and when the pressure increases, the temperature and pore size decrease. Isosteric heat of adsorption is in the range of −5.0 to −1.7 kJ/mol, which indicates that the adsorption behavior belongs to physical adsorption. The results of isosteric heat of adsorption show that strong energy exchange occurs in the H2-quartz system at the initial stage of adsorption, which may affect the stability of quartz. The average isosteric heat of adsorption linearly increases with temperature. However, the increasing rate of average isosteric heat of adsorption decreases with the increase in the pore size. Adsorption snapshots show most of the H2 distributed randomly and there is no obvious adsorption layer of H2 in the pores. Excess adsorption amount increases with the decrease in temperature and the increase in pressure and pore size. The change rate of excess adsorption amount with temperature increases with the increase in pressure. Similarly, with the increase in pressure, the change rate of excess adsorption amount with pore size decreases slowly at first, then increases rapidly, and finally decreases. The results are helpful to reveal the migration and formation of H2 reservoirs in the Earth’s interior.