Grand Canonical Monte Carlo Simulations Research Articles

Investigating adsorption properties of CO2 and CH4 in subbituminous coals from Mamu and Nsukka formations: a molecular simulation approach

AbstractThe study aimed to investigate the adsorption properties of methane (CH4) and carbon dioxide (CO2) in subbituminous coals from the Mamu and Nsukka formations, focusing on the CO2-Enhanced Coalbed Methane (ECBM) method. Proximate, ultimate, and FT-IR analyses determined the quality, age, and functional categories of these coals, confirming their subbituminous nature. Using molecular dynamics (MD) simulations, a unique amorphous subbituminous coal model was developed to study adsorption phenomena. Isosteric heat and adsorption isotherms for pure CO2 and CH4 were analyzed, alongside Grand Canonical Monte Carlo (GCMC) simulations to assess CO2 adsorption selectivity in a binary CO2 and CH4 mixture. Results showed that CO2 required more isosteric heat than CH4 in single-component scenarios and demonstrated stronger electrostatic interactions with heteroatom groups in the coal model, explaining its higher adsorption preference. In binary adsorption experiments, CO2 exhibited a higher affinity under specific conditions, particularly influenced by pressure variations. At lower pressures, CO2 selectivity decreased rapidly with increasing temperature, while at higher pressures, the influence of temperature diminished. These findings have established a theoretical and practical basis for optimizing CO2-ECBM extraction in Nigeria, highlighting the preferential adsorption of CO2 over CH4 in subbituminous coals from the Mamu and Nsukka formations under varying pressure and temperature conditions. Implementing CO2-ECBM extraction and storage in Nigeria could boost economic viability and help achieve net-zero goals, using insights from this study to guide policy development. Graphical Abstract

DFT-based, Monte Carlo and Grand Canonical Monte Carlo simulations of nitro-organic pollutants 4-nitrophenol, 2-nitrophenol, 9-nitroanthracene and nitrogen trifluoride interacting with water in zeolite imidazole framework (ZIF-8)

DFT-based, Monte Carlo and Grand Canonical Monte Carlo simulations of nitro-organic pollutants 4-nitrophenol, 2-nitrophenol, 9-nitroanthracene and nitrogen trifluoride interacting with water in zeolite imidazole framework (ZIF-8)

Stable heterometallic metal-organic frameworks and pellet composites for low-temperature natural gas storage

Liquefied natural gas coupled with adsorbed natural gas charging (LNG-ANG) offers an efficient solution for recycling boil-off gas, providing a promising strategy for the competent storage and transportation of natural gas. The key challenge in LNG-ANG coupling systems is identifying adsorbents that exhibit superior methane adsorption performance and excellent stability under cryogenic conditions (∼159 K). In this work, we systematically investigated the methane adsorption performance of a stable metal–organic framework, PCN-250-Fe2Ni, under LNG-ANG related conditions. The results demonstrated that PCN-250-Fe2Ni exhibited a high methane capacity of 286 cm3 (standard temperature and pressure, STP) cm−3 (0.227 g g−1) at 6 bar/159 K. Furthermore, the pellet composite of PCN-250-Fe2Ni and polyvinyl butyral also displayed a high methane adsorption capacity with excellent cycling stability. Combined with grand canonical Monte Carlo simulations, our findings revealed that the cage-type pores serve as initial methane adsorption sites, followed by the channel-type pores, both of which contribute to the framework’s high low-temperature methane storage performance at saturation.

Experimental and molecular simulation study of CO2 adsorption in ZIF-8: Atomic heat contributions and mechanism

We successfully synthesised ZIF-8 using the solvothermal method at room temperature to study CO2 adsorption storage at 273 and 298 K up to 35 bar. Characterisation methods such as BET, SEM-EDS, XRD, and TGA were used to measure the physical and composition properties of ZIF-8. Grand canonical Monte Carlo (GCMC) simulation was conducted to compare with experimental data and get inside of the CO2 adsorption mechanism by calculating the isosteric heat and its fluid–fluid and solid–fluid contributions. The second was also split into fluid–solid atom contributions to understand in detail the interaction between CO2 and ZIF-8. The analyses revealed that there are three main stages during the CO2 adsorption gas–solid atom contributions, developing, pore-filling and densification. During the developing and pore-filling stages the largest fluid–solid atom contribution to the isosteric heat is CO2-C2 interactions, indicating that the CO2 is adsorbed close to the hexagonal windows of the ZIF-8 structure, while during the densification stage the largest contribution is CO2-N interactions. Where C2 and N refers to C-atom and N-atom, respectively in NCH group of the solid framework. This is because CO2 changes its orientation to be able to accommodate more molecules in the pore cavity. This work provides a better understanding of the adsorption mechanism of CO2 on ZIF-8 and shows how molecular simulation can be used to improve the understanding gas adsorption storage on metal–organic frameworks.

Mechanistic effects of graphitization and oxygen functional groups on benzene competitive adsorption of porous carbon under high humidity conditions

Porous carbon is an ideal adsorbent for the elimination of volatile organic compounds (VOCs) attributed to their price, availability and excellent adsorption capacity. However, there are significant variation in the adsorption capacity and adsorption selectivity of different precursors for VOCs under humid conditions after modification because of the differences in their own structural properties. In this study, graphitized hydrophobic porous carbon with excellent specific surface area was successfully synthesized by selecting bamboo fiber, maize, coconut husk and coal as precursors and potassium hydroxide as an activator. Among them, the dynamic adsorption capacity of benzene in the sample with bamboo fiber as precursor was maintained at 74.7% under the high humidity condition (RH90%) compared with the dry state (RH0%). Grand Canonical Monte Carlo (GCMC) simulations and weak interaction force analyses showed that enhanced dispersion attraction between graphitized carbon surfaces and benzene molecules in comparison to disordered carbon surfaces. The existence of oxygen functional groups enhanced the interaction between porous carbon and water through hydrogen bonding leading to preferential adsorption of water molecules, which resulting in the decrease of their adsorption performance in wet condition. This research provided theoretical and experimental views of the effects of graphitization and oxygen functional groups on the competitive adsorption capture of benzene and water by porous carbon, which further provided a reliable approach to synthesizing porous carbon with high adsorption capture for benzene removal in high humidity environments.

A stable dual-function lanthanum MOF: Simultaneous CO2 capture and catalysis

Carbon dioxide (CO2) capture has become a hot topic in recent years because of global warming issues. However, most research has focused primarily on gas capture, with limited methods available for achieving both CO2 capture and conversion within a single material. Here, we synthesized FMU-101, a metal-organic framework (MOF) with metal-open sites, through the self-assembly of [1,1′-Biphenyl]-3,3′,5-tricarboxylic acid and lanthanide ions in a solvothermal environment. FMU-101 features hexagonal one-dimensional pores with a diameter of 1.4 nm. The presence of free dimethylamine cations and metal open sites in the channel contributes to its remarkable capability for selectively enriching CO2 from CO2/CH4 mixtures in dynamic breakthrough experiments. Furthermore, the metal-open sites in FMU-101 play a crucial role in CO2 fixation, serving as effective catalytic sites for converting the adsorbed CO2 into high-value chloropropylene carbonate, a versatile chemical intermediate. The segregation and conversion mechanisms were further elucidated through density-functional theory (DFT) calculations and Grand Canonical Monte Carlo (GCMC) simulations, which highlighted the critical role of metal-open sites in CO2 adsorption and transformation.

Computational Exploration of Adsorption-Based Hydrogen Storage in Mg-Alkoxide Functionalized Covalent-Organic Frameworks (COFs): Force-Field and Machine Learning Models.

Hydrogen is a clean-burning fuel that can be converted to other forms. of energy without generating any greenhouse gases. Currently, hydrogen is stored either by compression to high pressure (>700 bar) or cryogenic cooling to liquid form (<23 K). Therefore, it is essential to develop safe, reliable, and energy-efficient storage technology that can store hydrogen at lower pressures and temperatures. In this work, we systematically designed 2902 Mg-alkoxide-functionalized covalent-organic frameworks (COFs) and performed high-throughput (HT) computational screening for hydrogen storage applications at 111, 231, and 296 K. To accurately model the interaction between Mg-alkoxide sites and molecular hydrogen, we performed MP2 calculations to compute the hydrogen binding energy for different types of functionalized models, and the data were subsequently used to fit modified-Morse force field (FF) parameters. Using the developed FF models, we conducted HT grand canonical Monte Carlo (GCMC) simulations to compute hydrogen uptakes for both original and functionalized COFs. The generated data were subsequently used to evaluate the materials' gravimetric and volumetric storage performance at various temperatures (111, 231, and 296 K). Finally, we developed machine learning (ML) models to predict the hydrogen storage performance of functionalized structures based on the features of the original structures. The developed model showed excellent performance with a mean absolute error (MAE) of 0.061 wt % and 0.456 g/L for predicting the gravimetric and volumetric deliverable capacities, enabling a quick evaluation of structures in a hypothetical COF database. The screening results demonstrated that the Mg-alkoxide functionalization yields greater improvements in volumetric H2 storage capacities for COFs with smaller pores compared to those with larger (mesoporous) pores.

Dynamic CO2 separation performance of nano-sized CHA zeolites under multi-component gas mixtures

To identify and evaluate promising adsorbents for CO2 separation, we synthesized CHA zeolites with different cations (Na+, K+, Cs+) and crystal sizes (45 nm – CHA45 and 500 nm – CHA500), and evaluated their explored CO2 adsorption performance from CO2/N2/He and CO2/CH4/He mixtures. Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations predicted CO2, N2, and CH4 adsorption isotherms and CO2 mobilities, respectively, which were compared to experimental data. Breakthrough curve analysis was used to assess the CO2 dynamic adsorption performance. The breakthrough curve analysis shows the smaller crystal sizes (45 nm) enhance the CO2 separation due to shorter interacrystalline diffusion pathways. Notably, Cs-CHA45 removed 2.2 times more CO2 from CO2/N2/He than Cs-CHA500. K-CHA45 showed the highest CO2/N2 selectivity (108) and achieved 841mmol g−1 for CO2 capture from N2 and 721mmol g−1 for CO2 from CH4. These findings underscore the potential of CHA nanocrystals for effective CO2 separation in various applications.

High Volumetric and Gravimetric Acetylene Uptakes in a Cu-MOF with Tailored Cages.

NTUniv-80 exhibits record-high volumetric and gravimetric acetylene (C2H2) uptakes of 210 cm3 (STP) g-1 and 227 cm3 (STP) cm-3 at 295 K and 1 atm, respectively. Grand canonical Monte Carlo (GCMC) simulation indicates that those remarkable C2H2 uptakes are attributed to the open Cu2+ sites and tailored cages.

Synthesis and optimization of 3D porous polymers for efficient CO2 capture and H2 storage

In this study, a new porous organic polymer (KFUPM-CO2) with intrinsic nitrogen atoms as active sites for CO2 capture was optimized and synthesized via Friedel-Crafts alkylation of triptycene and 2,2-bipyridine. The porous polymer shows a high surface area of 1100 m2/g with a tuned microporosity of less than 1.2 nm, confirmed by NLDFT. KFUPM-CO2 showed a remarkable CO2 sorption capacity of 5.6 mmol/g at 273 K, 3.2 mmol/g at 298 K, and a pressure of 760 mmHg KFUPM-CO2 showed a high enthalpy of adsorption of 43.7 kJ/mol for CO2 with IAST selectivity of CO2/N2 of 127 at 273 K and 97 at 298 K on simulated flue gas composition. Additionally, KFUPM-CO2 exhibited an H2 storage capacity of 1.5 wt. % at 77 K and 860 mmHg Grand Canonical Monte Carlo (GCMC) simulations further revealed that KFUPM-CO2 was mainly stabilized by π-π intra-molecular interactions, and exhibited strong van der Waals attractions to CO2 molecules via the pyridyl nitrogen atoms, resulting in the rapid uptake. The combined advantages of binding 2,2-bipyridine with triptycene provided a robust porous polymer with abundant nitrogen sites, permanent porosity, and thermal stability, rendering KFUPM-CO2 an excellent candidate for CO2 capture and H2 storage technologies.

CO2 Utilization and Sequestration in Organic and Inorganic Nanopores During Depressurization and Huff-n-Puff Process.

CO2 injection in shale reservoirs is more suitable than the conventional recovering methods due to its easier injectivity and higher sweep efficiency. In this work, Grand Canonical Monte Carlo (GCMC) simulation is employed to investigate the adsorption/desorption behavior of CH4-C4H10 and CH4-C4H10-CO2 mixtures in organic and inorganic nanopores during pressure drawdown and CO2 huff and puff processes. The huff and puff process involves injecting CO2 into the micro- and mesopores, where the system pressure is increased during the huffing process and decreased during the puffing process. The fundamental mechanism of shale gas recovery using the CO2 injection method is thereby revealed from the nanopore-scale perspective. During primary gas production, CH4 is more likely to be produced as the reservoir pressure drops. On the contrary, C4H10 tends to be trapped in these organic nanopores and is hard to extract, especially from micropores and inorganic pores. During the CO2 huffing period, the adsorbed CH4 and C4H10 are recovered efficiently from the inorganic mesopores. On the contrary, the adsorbed C4H10 is slightly extracted from the inorganic micropores during the CO2 puffing period. During the CO2 puff process, the adsorbed CH4 desorbs from the pore surface and is thus heavily recovered, while the adsorbed C4H10 cannot be readily produced. During CO2 huff and puff, the recovery efficiency of CH4 is higher in the organic pores than that in the inorganic pores. More importantly, the recovery efficiency of C4H10 reaches the highest levels in both the inorganic and organic pores during the CO2 huff and puff process, suggesting that the CO2 huff and puff method is more advanced for heavier hydrocarbon recovery compared to the pressure drawdown method. In addition to CO2 storage, CO2 sequestration in the adsorbed state is safer than that in the free state. In our work, it was found that the high content of organic matter, high pressure, and small pores are beneficial factors for CO2 sequestration transforming into adsorbed state storage.

Accelerating Discovery of Mechanically Stable Metal-Organic Frameworks for Vinylidene Fluoride Storage by Active Learning.

Metal-organic frameworks (MOFs) are versatile nanoporous materials for a wide variety of important applications. Recently, a handful of MOFs have been explored for the storage of toxic fluorinated gases (Keasler et al. Science, 2023, 381, 1455), yet the potential of a great number of MOFs for such an environmentally sustainable application has not been thoroughly investigated. In this work, we apply active learning (AL) to accelerate the discovery of hypothetical MOFs (hMOFs) that can efficiently store a specific fluorinated gas, namely, vinylidene fluoride (VDF). First, a force field was developed for VDF and utilized to predict the working capacities (ΔN) of VDF in an initial data set of 4502 MOFs from the computation-ready experimental MOF (CoRE-MOF) database that successfully underwent featurization and grand-canonical Monte Carlo simulations. Next, the initial data set was diversified by Greedy sampling in an unexplored sample space of 119,387 hMOFs from the ab initio REPEAT charge MOF (ARC-MOF) database. A budget of 10,000 samples (i.e., <10% of total ARC-MOFs) was selected to train a random forest model. Then, ΔN in the unlabeled ARC-MOFs were predicted and top-performing ones were validated by simulations. Integrating with the stability requirement, mechanically stable ARC-MOFs were finally identified, along with high ΔN. Furthermore, by Pareto-Frontier analysis, we revealed that long linear linkers can enhance ΔN, while bulkier multiphenyl linkers or interpenetrated frameworks improve mechanical strength. From this work, we efficiently discover top-performing MOFs for VDF storage by AL and also demonstrate the importance of integrating stability to identify stable promising MOFs for a practical application.

Molecular simulations of increased thermal energy storage in metal–organic heat carriers with R1234ze(E)/R32 mixtures combined with IRMOF-1

Metal-organic heat carrier (MOHC) nanofluids offer a promising solution to enhance the efficiency of Organic Rankine Cycle systems. In this study, we developed a computational model to assess the thermal energy storage capacity of MOHC nanofluids using a base fluid mixture of R1234ze(E) and R32 refrigerants. Through Grand Canonical Monte Carlo and molecular dynamics simulations, we examined the adsorption characteristics, desorption heat, and thermodynamic properties of MOHCs. Our findings reveal that R32 molecules are preferentially adsorbed in IRMOF-1 compared to R1234ze(E), with adsorption selectivity of R32 over R1234ze(E) increasing under higher adsorption pressures. When the temperature during the endothermic process surpasses the phase transition point of the base fluid, the latent heat of phase transition can be fully exploited to enhance energy storage. Moreover, the inclusion of IRMOF-1 nanoparticles significantly improves the energy storage properties of both R32 and R1234ze(E), as well as their mixtures. The energy storage enhancement provided by IRMOF-1 is particularly pronounced under high working pressures and low temperature differences. These insights offer valuable guidance for selecting appropriate base fluids in MOHC systems, thereby optimizing the utilization of low-grade energy sources.

Phase behavior analysis of methane confined in nanopores using molecular simulation

Interest in the phase behavior of hydrocarbons in shale reservoirs has grown in recent years. Petroleum fluid phase behavior has been observed to differ significantly between conventional reservoirs and shale reservoirs. Within shale reservoirs, notable surface-fluid interactions can lead to non-uniform molecule distribution and an alteration in fluid phase behavior, primarily caused by the existence of nano-scale porous materials. In this work, we study the phase behavior of methane in single cylindrical pore models. We apply the gauge Gibbs ensemble Monte Carlo (gauge-GEMC) simulation technique to investigate the phase behavior of methane in 4–10 nm single nanopores and calculate the saturation pressures at various temperatures using the grand canonical Monte Carlo (GCMC) simulation technique. A shift in the phase diagram has been found for methane in nanopores. As pore size decreases, the shift becomes more significant.

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.

Multilayer Adsorption Characteristics of CO2 in Organic Nanopores with Different Pore Sizes: Molecular Simulation and Ono-Kondo Lattice Model.

Shale contains numerous organic micropores with significant potential for CO2 storage. To precisely evaluate the CO2 storage potential of shale reservoirs, it is essential to accurately quantify the adsorption of CO2 within these pores. This study used Grand Canonical Monte Carlo (GCMC) molecular simulations to analyze the CO2 adsorption behavior in organic micropores of varying sizes. The study clarified the number and width of the CO2 adsorption layers in micropores of various sizes and proposed a method for segmenting the multilayer adsorption structure. Additionally, the classic Ono-Kondo lattice (OK) model was extended to characterize pore-filling adsorption, incorporating solid-gas and gas-gas interactions. Accurate characterization of CO2 multilayer adsorption and precise calculation of CO2 absolute adsorption in micropores were achieved. Results indicate that CO2 exhibits pore-filling adsorption behavior in organic micropores, forming a multilayer adsorption structure governed by the pore size. Following symmetry principles, the adsorption layer structure in organic micropores can be simplified to a maximum of three layers. When only one adsorption layer forms, its width equals the gas-accessible pore size. For two or more layers, the width of the original layer stabilizes as additional layers form. The stable adsorption layer widths, from nearest to farthest from the pore wall, are 0.33, 0.45, and 0.39 nm. The improved OK model accurately describes CO2 excess and absolute adsorption isotherms across different pore sizes and calculates the CO2 density in each adsorption layer, showing high consistency with GCMC simulation results. These findings highlight the importance of understanding the CO2 multilayer adsorption structure for accurately estimating CO2 adsorption in organic micropores.

In-situ nitrogen-doped porous carbon derived from penicillin mycelial residue for CO2 adsorption and adsorption mechanism investigation

The in-situ nitrogen-doped porous carbon materials was synthesized using penicillin mycelial residue (PMR) as the sole endogenous nitrogen-rich precursor through a two-step process applied for CO2 adsorption. Precise control over the structural properties and CO2 adsorption performance of the porous carbon was achieved by varying the KOH dosage and activation temperature. The porous carbon prepared under mild activation conditions (600 ℃, KOH/BC = 1) exhibited high nitrogen content and abundant ultramicroporous structures (pore size ≤ 0.7 nm), and demonstrated outstanding adsorption performance. The CO2 adsorption capacities reached 6.55 mmol/g at 0 ℃ and 3.48 mmol/g at 25 ℃, showing promising CO2/N2 selectivity and robust cyclic adsorption stability. Quantitative structure–activity relationship analysis displayed a strong correlation between adsorption density, CO2/N2 selectivity, and nitrogen content. Density functional theory calculations further confirmed that nitrogen-doping, especially pyrrolic-N, serves as favorable structural sites for CO2 adsorption. Additionally, Grand Canonical Monte Carlo simulations verified that the ultramicroporous structures significantly enhances CO2 adsorption due to their strong affinity for CO2. This study provides an economic strategy for the preparation of in-situ nitrogen-doped porous carbon with enriched micropore using PMR, highlighting their promising performances in CO2 adsorption, synchronously extending the harmless treatment and resource utilization of PMR to demonstrate a sustainable approach for environmental remediation.

Boron nitride graphite intercalated with carbon-boron-nitride fullerenes for enhanced hydrogen storage

The hydrogen storage of boron nitride graphite intercalated with carbon-boron-nitride fullerenes was investigated using density functional theory and Grand Canonical Monte Carlo simulations. At 77 K and 30 MPa, the optimized structures C14(BN)23-inserted BN graphite material achieved a gravimetric hydrogen adsorption of 6.39 wt% and a volumetric adsorption of 0.07 kg/L, surpassing the U.S. Department of Energy’s targets of 5.5 wt% and 0.04 kg/L, respectively. This improved performance is attributed to the stronger adsorption affinity of BN atoms and the increased lattice constants of the material. These findings offer promising avenues for the development of advanced hydrogen storage materials.

MOFs with the Stability for Practical Gas Adsorption Applications Require New Design Rules.

Metal-organic frameworks (MOFs) have been widely studied for their ability to capture and store greenhouse gases. However, most computational discovery efforts study hypothetical MOFs without consideration of their stability, limiting the practical application of novel materials. We overcome this limitation by screening hypothetical ultrastable MOFs that have predicted high thermal and activation stability, as judged by machine learning (ML) models trained on experimental measures of stability. We enhance this set by computing the bulk modulus as a measure of mechanical stability and filter 1102 mechanically robust hypothetical MOFs from a database of ultrastable MOFs (USMOF DB). Grand Canonical Monte Carlo simulations are then employed to predict the gas adsorption properties of these hypothetical MOFs, alongside a database of experimental MOFs. We identify privileged building blocks that lead MOFs in USMOF DB to show exceptional working capacities compared to the experimental MOFs. We interpret these differences by training ML models on CO2 and CH4 adsorption in these databases, showing how poor model transferability between data sets indicates that novel design rules can be derived from USMOF DB that would not have been gathered through assessment of structurally characterized MOFs. We identify geometric features and node chemistry that will enable the rational design of MOFs with enhanced gas adsorption properties in synthetically realizable MOFs.

Constructing CO2 capture nanotraps via tentacle-like covalent organic frameworks towards efficient CO2 separation in mixed matrix membrane

The structure and morphology of fillers are crucial factors in the process of CO2 separation within mixed matrix membranes (MMMs). In this study, the tentacle-like covalent organic framework (COF) as a filler was incorporated into the Pebax matrix for CO2/CH4 separation. The COF has abundant Lewis base sites (O atom and N atom) and porous pores, thereby constructing efficient CO2 capture nanotraps in the MMMs. The CO2 capture nanotraps facilitate the CO2 transport in the MMMs, and this can be verified by the Grand Canonical Monte Carlo (GCMC) simulation and density functional theory (DFT) calculation. Simultaneously, the CO2 capture nanotraps are distributed on the surface of tentacle-like COF, which is conducive to strengthening CO2 capture ability. Therefore, Pebax/COF MMMs exhibited superior CO2 gas separation performance compared to the pure Pebax membrane. Among them, the MMM with 3 wt% COF loading displayed the highest CO2 gas separation performance, exhibiting permeability and selectivity that were 73.4% and 32.9% higher than the pure Pebax membrane, respectively. Thus, CO2 capture nanotraps constructed in the MMMs via tentacle-like COF showed a promising potential for CO2 separation.