Grand Canonical Monte Carlo Simulations Research Articles

Tuning the hydrogen storage capacity of MOF‐650 by Mg2+/Ca2+ substitution and B, N co‐doped atoms: Grand canonical Monte Carlo simulation and periodic density functional theory

AbstractThis study used periodic density functional theory and grand canonical Monte Carlo simulations to investigate the effects of the co‐doping of B and N atoms and substituting Zn2+ with Mg2+ or Ca2+ in the organic linker groups of MOF‐650. The functionalization increased the polarity of the organic groups, stabilizing the interaction between the MOF and hydrogen molecules. The highest average binding energy of the adsorbed hydrogen in MOF‐650 NB‐C7‐azulene‐Mg was calculated to be −4.75 to 5.40 kcal/mol for the α adsorption sites. Using the substitution of NB azulene and metal cations being Mg2+ or Ca2+, The hydrogen storage capacity of functionalized MOF‐650 was increased to 22 mg/g at 90 bar/298 K, implying the modification strategy of MOF‐650 would strengthen the interaction between MOF frameworks and hydrogen molecules.

Effects of Fluorinated Functionalization of Linker on Quercetin Encapsulation, Release and Hela Cell Cytotoxicity of Cu-Based MOFs as Smart pH-Stimuli Nanocarriers.

Controlled delivery of target molecules is required in many medical and chemical applications. For such purposes, metal-organic frameworks (MOFs), which possess desirable features such as high porosity, large surface area, and adjustable functionalities, hold great potential as drug carriers. Herein, Quercetin (QU), as an anticancer drug, was loaded on Cu2 (BDC)2 (DABCO) and Cu2 (F4 BDC)2 )DABCO) MOFs (BDC=1,4-benzenedicarboxylate and DABCO=1,4-diazabicyclo[2.2.2]octane). As these Cu-MOFs have a high surface area, an appropriate pore size, and biocompatible ingredients, they can be utilized to deliver QU. The loading efficiency of QU in these MOFs was 49.5 % and 41.3 %, respectively. The drug-loaded compounds displayed sustained drug release over 15 days, remarkably high drug loading capacities and pH-controlled release behavior. The prepared nanostructures were characterized by different characterization technics including FT-IR, PXRD, ZP, TEM, FE-SEM, UV-vis, and BET. In addition, MTT assays were carried out on the HEK-293 and HeLa cell lines to investigate cytotoxicity. Cellular apoptosis analysis was performed to investigate the cell death mechanisms. Grand Canonical Monte Carlo simulations were conducted to analyze the interactions between MOFs and QU. Moreover, the stability of MOFs was also investigated during and after the drug release process. Ultimately, kinetic models of drug release were evaluated.

Grand Canonical Monte Carlo Simulation Experiences of Methane and Ethane Adsorption Behaviors on Simplified Organic Shale Formed by Graphene Layering

Grand Canonical Monte Carlo Simulation Experiences of Methane and Ethane Adsorption Behaviors on Simplified Organic Shale Formed by Graphene Layering

Development of atomistic graphene models for H2 adsorption from experimental data and Monte Carlo simulations

The development of adsorbent materials for the storage of hydrogen is a major research topic since this could allow effective low volume storage for mobile applications. Few-layer graphene (FLG) is a candidate to work as a template for adsorptive materials. In order to gain insight into the adsorption of hydrogen on FLG a series of Grand Canonical Monte Carlo simulations were performed to analyze the effect of the pore size and the number of layers. A semiempirical and easy-to-implement model was developed to correlate hydrogen adsorption isotherms with the morphological characteristics of the material, such as, the characteristic number of layers and the pore size. A correlation between the adsorption isotherms with the number of layers and the characteristic pore size was developed and validated against available experimental data at different temperatures showing its applicability to the description of FLG.

Nitrogen-doped carbon particles with distinctive ethylene adsorption selectivity for efficient ethylene/acetylene separation

Separation of ethylene/acetylene (C2H4/C2H2) mixtures with C2H4-selective adsorbents is of economics and energy efficiency to purify crude C2H2 from methane pyrolysis or partial oxidation (POX) process. Herein, a systematic study was carried out to investigate the structural properties and C2H4/C2H2 separation performance of novel nitrogen-doped carbon particles, as well as the mechanism of preferentially adsorbing C2H4 over C2H2 through the Grand Canonical Monte Carlo (GCMC) simulations. The nitrogen-doped carbon particles derived from coconut shell and metronidazole present regular particle sizes centering at 710 μm and excellent crushing strength of 89 N. Well-developed microporosity with pore dimension mainly ranging in 0.54–0.68 nm, and fine-tuning surface chemistry with abundant nitrogen-containing species (pyridinic N, pyrrolic N and graphitic N) were observed in nitrogen-doped carbon particles. Interestingly, nitrogen-doped carbon particles exhibit preferential adsorption of C2H4 over C2H2, and the IAST-predicted selectivity of 1.5-N-CP reaches as high as 5.2 for C2H4/C2H2 (1/9) mixture at 1.0 bar and 25 °C. Remarkably, the separation stability and recyclability with complete separation for C2H4/C2H2 were well maintained during cyclic dynamic breakthrough experiments. GCMC simulation results demonstrate that the graphitic N with great binding energy (−22.61 kJ/mol for C2H4 and −19.87 kJ/mol for C2H2) favors the adsorption of both C2H4 and C2H2. The pore dimension ranging 0.54–0.68 nm, together with pyridinic N and pyrrolic N species significantly enhance the separation of C2H4/C2H2 through the large difference in adsorption interactions between C2H4 and C2H2. Therefore, the nitrogen-doped carbon particles have the excellent application accessibility in purifying C2H2 from C2H4/C2H2 mixture.

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.

Molecular simulation of methane/ethane mixture adsorption behavior in shale nanopore systems with micropores and mesopores

Shale formation has a broad pore size distribution with both micropores (<2 nm) and mesopores (2–50 nm) in the kerogen matrix in addition to the macropores and fractures. Methane and ethane are two primary hydrocarbon species of shale gas, and the competitive sorption behavior in kerogen micropores and mesopores is not well understood. In this work, grand canonical Monte Carlo (GCMC) was used to study the sorption behavior of methane, ethane, and their binary mixtures (from 1:9 to 9:1) in kerogen nanopore systems with micropores and mesopores at 327 K and pressures ranging from 1 to 50 MPa. Three zones (Zone I: free gas, Zone II: adsorbed gas, and Zone III: absorbed gas) were defined to describe the sorption in micropores and mesopores. The results show different selectivity characteristics of ethane over methane for three different zones. The mass densities of gas molecules in different zones were obtained, which can be used for gas-in-place estimation. The calculated sorption isotherms of shale samples show reasonably good agreement with previous experiments. We show that the Langmuir model can be used to describe the absolute sorption isotherms of pure methane and ethane. For binary mixtures, the absolute sorption of individual gases predicted by the multicomponent Langmuir (ML) model shows a deviation from GCMC simulation results. However, with two correction coefficients, the modified ML models match the absolute sorption amount from the GCMC very well. Finally, a micropore-mesopore (MM) model was derived for the excess-absolute sorption relationship, which significantly improves the prediction accuracy of the absolute sorption in shale gas systems. This research highlights the importance of using kerogen nanopore systems with both micropores and mesopores.

Direct prediction of gas adsorption via spatial atom interaction learning

Physisorption relying on crystalline porous materials offers prospective avenues for sustainable separation processes, greenhouse gas capture, and energy storage. However, the lack of end-to-end deep learning model for adsorption prediction confines the rapid and precise screen of crystalline porous materials. Here, we present DeepSorption, a spatial atom interaction learning network that realizes accurate, fast, and direct structure-adsorption prediction with only information of atomic coordinate and chemical element types. The breakthrough in prediction is attributed to the awareness of global structure and local spatial atom interactions endowed by the developed Matformer, which provides the intuitive visualization of atomic-level thinking and executing trajectory in crystalline porous materials prediction. Complete adsorption curves prediction could be performed using DeepSorption with a higher accuracy than Grand canonical Monte Carlo simulation and other machine learning models, a 20-35% decline in the mean absolute error compared to graph neural network CGCNN and machine learning models based on descriptors. Since the established direct associations between raw structure and target functions are based on the understanding of the fundamental chemistry of interatomic interactions, the deep learning network is rationally universal in predicting the different physicochemical properties of various crystalline materials.

Ab initio selection of zeolite topology for biomass conversion to para-xylene based on transition state selectivity

Recent reports have pointed out a sustainable and highly selective formation route via the Diels–Alder (DA) cycloaddition between biomass-derived 2, 5-dimethylfuran (DMF) and ethene over zeolitic catalysts to produce para-xylene (p-xylene). Here, a systematic multi-scale simulation was carried out to identify candidate zeolite frameworks with potentially better catalytic activities than previously reported catalysts, through a combination of “ab initio” synthesis, thermodynamic and kinetic analysis, and adsorption/diffusion simulations. We first screened representative zeolites based on the limiting dimensions of their voids (windows, cages, channels) for reactants and products, the extent of stabilization of the key transition states by organic structure directing agents, and the synthesis difficulty informed by literature knowledge. Subsequently, the intrinsic and apparent free energy barriers of the rate-determining step (i.e., cycloaddition) obtained from density functional theory calculations were used to predict reaction kinetics of the potentially useful zeolites. Finally, three final candidates (MOR, MOZ, and IFR) and two experimentally validated zeolites (FAU and BEA) were employed to compare the adsorption and diffusion performance of DMF and p-xylene as the final criterion by grand canonical Monte Carlo and molecular dynamics simulations. In summary, MOR shows the fastest diffusion, IFR shows the lowest apparent energy barrier, and MOZ shows the lowest intrinsic energy barrier. Altogether, this study not only predicts MOR, IFR, and MOZ zeolites to have a good catalytic performance for the DA-dehydration process of DMF and ethene to p-xylene but also illustrates the potential of ab initio selection, through combined theoretical assessments of adsorption, reaction and diffusion, for the rational selection and design of optimal catalysts for targeted catalytic transformations.

Hydrogen permeability of polyamide 6 as the liner material of Type Ⅳ hydrogen storage tanks: A molecular dynamics investigation

To attain a lightweight structure with high pressure and a high hydrogen storage mass ratio, the type IV hydrogen storage tank is the most popular choice for many fuel cell vehicle enterprises. Using polymer as the liner material prevents hydrogen embrittlement and hydrogen-induced damage of the tanks, but hydrogen permeation is inevitable. Within the service conditions (233–358 K, 0–87.5 MPa) of the Type-IV tanks, the dissolution and diffusion behaviors of H2 in polyamide 6 are comprehensively explored for the first time through the molecular dynamics and Grand Canonical Monte Carlo simulations in this study. The diffusion mechanism of H2 in polyamide 6 is further revealed. The results show that both the diffusion and permeability coefficients have positive correlations with temperature, whereas the opposite is true for the solubility coefficient. These relationships are all consistent with Arrhenius's law in the temperature range, although multiple Arrhenius regions are needed to describe them. A slight decrease in the diffusion and permeability coefficients is observed with increasing pressure. However, this effect is not as significant as that of temperature and can be ignored when the pressure range is narrow enough. The “hopping” mechanism can be used to describe the diffusion of H2 in polyamide 6, where the continuous vibrations and “hopping” allow the diffusion of H2 molecules. These findings will contribute to a more comprehensive understanding of the permeation behavior of H2 in polyamide 6 and evaluate the gas barrier property of the material in practical applications.

Solvent-Directed Construction of a Nanoporous Metal-Organic Framework with Potential in Selective Adsorption and Separation of Gas Mixtures Studied by Grand Canonical Monte Carlo Simulations.

In this report, a microporous metal-organic framework of [Ca(TDC)(DMA)]n (1) and a two-dimensional coordination polymer of [Ca(TDC)(DMF)2 ]n (2), (TDC2- =Thiophene-2,5-dicarboxylate, DMA=N, N'-dimethylacetamide and DMF=N, N'-dimethylformamide) based on Ca(II) were designed by the effect of solvent, and X-ray analysis was performed for the single crystals of 1 and 2. Then, compound 1 was synthesized in three different methods and identified with a set of analyses. Compared to other adsorbents, MOFs are widely used in the field of adsorption and separation of various gases due to a series of distinctive features such as diverse and adjustable structures pores with different dimensions, high porosity and surface area with regular distribution of active sites. Therefore, the ability of 1 to uptake single gases (CH4 , CO2 , C2 H2 , H2, and N2 ) and separation of several binary mixtures of gases (CO2 /CH4 , CO2 /N2 , CO2 /H2 and CO2 /C2 H2 ), were investigated using Grand Canonical Monte Carlo simulations. Volumetric and gravimetric adsorption isotherms in various operating conditions, the isosteric heat of adsorption (qst ), the chemical potential for each thermodynamic state, and snapshots during the simulation process were reported in all cases. The results obtained from the adsorption simulation indicate that compound 1 has a high capacity for uptake of H2 (16 mmol g-1 ) and N2 (12.5 mmol g-1 ), CO2 (6.6 mmol g-1 ), C2 H2 (5 mmol g-1 ) and CH4 (1.5 mmol g-1 ) gases at 1 bar. It also performs well in separating CO2 in binary mixtures, which can be attributed to the presence of open metal sites in nodes of 1 and their electrostatic tendency to interact with CO2 containing the higher quadrupole dipole moment compared to other components of the mixture.

Theoretical Investigation of Inorganic Particulate Matter: The Case of Water Adsorption on a NaCl Particle Model Studied Using Grand Canonical Monte Carlo Simulations

Sodium chloride (NaCl) represents the principal component of atmospheric particulates of marine origin. To gain a molecular-level understanding of the adsorption process of water vapor on the NaCl surface, Monte Carlo simulations performed in the Grand Canonical ensemble were carried out, considering the water adsorption at different water pressures on a NaCl(001) surface. The calculated adsorption isotherm shows four different regions, whose coverages correspond to those of the low-, transition-, high-, and pre-solution-coverage regions experimentally observed. Detailed analysis reveals how the structure of the adsorbed water molecules (islands, layer, and multi-layer) changes depending on water pressure, and how their orientation with respect to the surface varies with the distance from the surface. This detailed information further supports the picture coming from previous experimental IR absorption spectroscopy studies.

CO2 storage in organic nanopores with varying widths: Molecular simulation and simplified local density model

Accurately characterizing CO2 adsorption behavior in organic nanopores is a prerequisite for estimating CO2 storage capacity in shale reservoirs with complex pore structures. This study employs grand canonical Monte Carlo (GCMC) molecular simulations to investigate the CO2 adsorption characteristics in organic nanopores with varying widths over a wide range of temperatures and pressures. Based on GCMC simulations, the pore width in the simplified Local-Density (SLD) adsorption model is related to key adsorption parameters, enabling the SLD model to evaluate CO2 storage density rapidly and accurately in organic nanopores under complex reservoir conditions. The research findings suggest that the features of CO2 excess adsorption curves are mainly influenced by temperature and the number of adsorption layers. Higher temperatures and increased adsorption layers result in higher pressure requirements to achieve the CO2 excess adsorption peak. Under high pressures, the number of adsorption layers plays a critical role in enhancing the adsorption capacity. Due to the constraints of pore size, there are fewer adsorption layers in micropores, leading to higher CO2 excess adsorption in mesopores than in micropores under high pressures. In the SLD model, the key parameter Λb decays exponentially with the increase of pore width. The average density of CO2 in the nanopores calculated by the modified SLD model is in good agreement with the simulation results. Finally, the research reveals that smaller organic nanopore widths result in higher CO2 densities, with limited sensitivity to temperature and pressure variations. Low pressure and high temperature reservoir conditions are unfavorable for CO2 storage, but adsorption significantly enhances CO2 storage density in nanopores, particularly in micropores.

Investigation of the effect of the key pore size on the radon adsorption performance by combining grand canonical Monte Carlo and activated carbon modification experiments

Radon (Rn) is an important contributing factor to lung cancer. Activated carbon (AC) is currently the only Rn adsorbent for industrial applications. However, the effect of the key pore size of AC on Rn adsorption remains unclear, and enhancement of the Rn adsorption performance when using AC is still a challenge. In this work, grand canonical Monte Carlo (GCMC) simulations were performed to simulate the Rn adsorption ability of AC with different pore sizes. The adsorption selectivity of AC with pore sizes from 0.42 nm to 0.60 nm for Rn in the atmospheric environment was much greater than that for nitrogen and oxygen. The Rn adsorption performance was also investigated using KOH-modified activated carbon (KAC) with different pore sizes experimentally prepared using high-temperature roasting. The results showed that when the pore volume of KAC was significantly increased to approximately 0.55 nm, the Rn adsorption performance was obviously improved. Its adsorption coefficient reached 6.50 ± 0.11 m3 kg−1, which was 46.7 % higher than that of AC. After heating and regeneration in air, the Rn adsorption performance of KAC was basically unchanged. Combined with the comparative analysis using theoretical and experimental results, the relationship between the Rn adsorption performance of KAC and the pore volume at 0.55 nm is determined, and the accuracy of the GCMC calculation results was substantiated. This research provides a theoretical basis and an experimental method for improving the Rn adsorption performance of AC.

Rational Design of Porous Ionic Liquids for Coupling Natural Gas Purification with Waste Gas Conversion

AbstractRemoval of trace impurities for natural gas purification coupled with waste gas conversion is highly desired in industry. We here report a type of porous ionic liquids (PILs) that can realize the continuous flow separation of CH4/CO2/H2S and the conversion of the captured H2S to useful products. The PILs are synthesized through a step‐by‐step surface modification of ionic liquids (ILs) onto UiO‐66‐OH nanocrystals. The introduction of free tertiary amine groups on the nanocrystal surface endows these PILs with an exceptional ability to enrich H2S from CO2 and CH4 with impressive selectivity, while the permanent pores of UiO‐66‐OH act as containers to store an exceptionally higher amount of the selectively captured H2S than the corresponding nonporous ILs. Simultaneously, the tertiary amines as dual functional moieties offer effective catalytic sites for the conversion of the H2S stored in PILs into 3‐mercaptoisobutyric acid, a key intermediate required for the synthesis of Captopril (an antihypertensive drug). Molecular dynamics, density functional theory calculations and Grand Canonical Monte Carlo simulations help understand both the mechanisms of separation and catalysis performance, confirming that the tertiary amines as well as the permanent pores in UiO‐66‐OH play vital roles in the whole procedure.

Rational Design of Porous Ionic Liquids for Coupling Natural Gas Purification with Waste Gas Conversion.

Removal of trace impurities for natural gas purification coupled with waste gas conversion is highly desired in industry. We here report a type of porous ionic liquids (PILs) that can realize the continuous flow separation of CH4 /CO2 /H2 S and the conversion of the captured H2 S to useful products. The PILs are synthesized through a step-by-step surface modification of ionic liquids (ILs) onto UiO-66-OH nanocrystals. The introduction of free tertiary amine groups on the nanocrystal surface endows these PILs with an exceptional ability to enrich H2 S from CO2 and CH4 with impressive selectivity, while the permanent pores of UiO-66-OH act as containers to store an exceptionally higher amount of the selectively captured H2 S than the corresponding nonporous ILs. Simultaneously, the tertiary amines as dual functional moieties offer effective catalytic sites for the conversion of the H2 S stored in PILs into 3-mercaptoisobutyric acid, a key intermediate required for the synthesis of Captopril (an antihypertensive drug). Molecular dynamics, density functional theory calculations and Grand Canonical Monte Carlo simulations help understand both the mechanisms of separation and catalysis performance, confirming that the tertiary amines as well as the permanent pores in UiO-66-OH play vital roles in the whole procedure.

Fabrication of Pillar‐Cage Fluorinated Anion Pillared Metal–Organic Frameworks via a Pillar Embedding Strategy and Efficient Separation of SO2 through Multi‐Site Trapping

AbstractFlue gas desulfurization is crucial for both human health and ecological environments. However, developing efficient SO2 adsorbents that can break the trade‐off between adsorption capacity and selectivity is still challenging. In this work, a new type of fluorinated anion‐pillared metal–organic frameworks (APMOFs) with a pillar‐cage structure is fabricated through pillar‐embedding into a highly porous and robust framework. This type of APMOFs comprises smaller tetrahedral cages and larger icosahedral cages interconnected by embedded [NbOF5]2− and [TaOF5]2− anions acting as pillars. The APMOFs exhibits high porosity and density of fluorinated anions, ensuring exceptional SO2 adsorption capacity and ultrahigh selectivity for SO2/CO2 and SO2/N2 gas mixtures. Furthermore, these two structures demonstrate excellent stability towards water, acid/alkali, and SO2 adsorption. Cycle dynamic breakthrough experiments confirm the excellent separation performance of SO2/CO2 gas mixtures and their cyclic stability. SO2‐loaded single‐crystal X‐ray diffraction, Grand canonical Monte Carlo (GCMC) simulations combined with density functional theory (DFT) calculations reveal the preferred adsorption domains for SO2 molecules. The multiple‐site host–guest and guest‐guest interactions facilitate selective recognition and dense packing of SO2 in this hybrid porous material. This work will be instructive for designing porous materials for flue gas desulfurization and other gas‐purification processes.

Fabrication of Pillar-Cage Fluorinated Anion Pillared Metal-Organic Frameworks via a Pillar Embedding Strategy and Efficient Separation of SO2 through Multi-Site Trapping.

Flue gas desulfurization is crucial for both human health and ecological environments. However, developing efficient SO2 adsorbents that can break the trade-off between adsorption capacity and selectivity is still challenging. In this work, a new type of fluorinated anion-pillared metal-organic frameworks (APMOFs) with a pillar-cage structure is fabricated through pillar-embedding into a highly porous and robust framework. This type of APMOFs comprises smaller tetrahedral cages and larger icosahedral cages interconnected by embedded [NbOF5]2- and [TaOF5]2- anions acting as pillars. The APMOFs exhibits high porosity and density of fluorinated anions, ensuring exceptional SO2 adsorption capacity and ultrahigh selectivity for SO2/CO2 and SO2/N2 gas mixtures. Furthermore, these two structures demonstrate excellent stability towards water, acid/alkali, and SO2 adsorption. Cycle dynamic breakthrough experiments confirm the excellent separation performance of SO2/CO2 gas mixtures and their cyclic stability. SO2-loaded single-crystal X-ray diffraction, Grand canonical Monte Carlo (GCMC) simulations combined with density functional theory (DFT) calculations reveal the preferred adsorption domains for SO2 molecules. The multiple-site host-guest and guest-guest interactions facilitate selective recognition and dense packing of SO2 in this hybrid porous material. This work will be instructive for designing porous materials for flue gas desulfurization and other gas-purification processes.

Experimental Measurements and Molecular Simulation of Carbon Dioxide Adsorption on Carbon Surface

Summary Geological sequestration of carbon dioxide (CO2) in depleted gas reservoirs represents a cost-effective solution to mitigate global carbon emissions. The surface chemistry of the reservoir rock, pressure, temperature, and moisture content are critical factors that determine the CO2 adsorption capacity and storage mechanisms. Shale-gas reservoirs are good candidates for this application. However, the interactions between CO2 and organic content still need further investigation. The objectives of this paper are to (i) experimentally evaluate the adsorption isotherm of CO2 on activated carbon, (ii) quantify the nanoscale interfacial interactions between CO2 and the activated carbon surface using Monte Carlo (MC) and molecular dynamic (MD) simulations, (iii) evaluate the modeling reliability using experimental measurements, and (iv) quantify the influence of temperature and geochemistry on the adsorption behavior of CO2 on the surface of activated carbon. These objectives aim at obtaining a better understanding of the behavior of CO2 injection and storage in the kerogen structure of shale-gas formations, where activated carbon is used as a proxy for thermally mature kerogen. We performed experimental measurements, grand canonical Monte Carlo (GCMC) simulations, and MD simulations of CO2 adsorption and diffusion on activated carbon. The experimental work involved measurements of the high-pressure adsorption capacity of activated carbon using pure CO2 gas at a temperature of 300 K. The simulation work started with modeling and validating an activated carbon structure by calibrating the GCMC simulations with experimental CO2 adsorption measurements. Then, we extended the simulation work to quantify the adsorption isotherms at a temperature range of 250–500 K and various surface chemistry conditions. Moreover, CO2 self-diffusion coefficients were quantified at gas pressures of 0.5 MPa, 1 MPa, and 2 MPa using MD simulations. The experimental results showed a typical CO2 excess adsorption trend for the nanoporous structures, with a density of the sorbed gas phase of 504.76 kg/m3. The simulation results were in agreement with experimental adsorption isotherms with a 10.6% average absolute relative difference. The self-diffusion results showed a decrease in gas diffusion with increasing pressure due to the increase in the adsorbed gas amount. Increasing the simulation temperature from 300 K to 400 K led to a decrease in the amount of adsorbed CO2 molecules by about 87% at 2 MPa pressure. Finally, the presence of charged functional groups (e.g., hydroxyl–OH and carboxyl–COOH) led to an increase in the adsorption of CO2 gas to the activated carbon surface. The outcomes of this paper provide new insights about the parameters affecting CO2 adsorption and sequestration in depleted shale-gas reservoirs. This in turn helps in screening the candidate shale-gas reservoirs for carbon capture, sequestration, and storage to maximize the CO2 storage capacity.

Molecular Simulation of Adsorption and Diffusion of Methane and Ethane in Kaolinite Clay under Supercritical Conditions: Effects of Water and Temperature

Grand Canonical Monte Carlo (GCMC) simulation and Molecular Dynamics (MD) simulations were used to study the effects of temperature (310 K to 400 K), pressure (≤30 MPa) and water content (0 molecule/nm3 to 9 molecule/nm3) on the adsorption and diffusion behavior of CH4 and C2H6 in 3 nm kaolinite slit under supercritical conditions. The obtained adsorption capacity, isosteric adsorption heat, concentration distribution and diffusion coefficient were analyzed and compared. The simulation results show that the adsorption capacity of C2H6 is higher under low pressure conditions, and the adsorption capacity of CH4 is higher under high pressure conditions due to the small molecular radius and increased adsorption space. The addition of water molecules and the increase in temperature will reduce the adsorption capacity and isosteric adsorption heat of the two gases. We analyzed the changes in Langmuir volume and Langmuir pressure of the two gases under different temperature and water content conditions. The addition of water molecules and the increase in temperature will reduce the saturation adsorption capacity (which has a greater effect on C2H6) and the adsorption rate of the two gases in the kaolinite slit. The water molecules occupy the adsorption site of the gas molecules (limiting the diffusion of the gas molecules), which reduces the interaction between gas molecules and the wall surface, thus altering the distribution of the two gases in the slit. The increase in temperature will accelerate the oscillation of the gas molecules, increasing diffusion, and also leads to a reduction in the peak value of the adsorption peaks of the two gases.