Grand Canonical Monte Carlo Simulations Research Articles

Competitive Adsorptive Mechanism of H2/N2 in LTA/FAU Zeolites by Molecular Simulations and Experiments.

For industrial tail gas to be converted into high-purity hydrogen, the H2-N2 mixture needs to be separated efficiently. This work examined the adsorption characteristics and competitive mechanisms of H2 and N2 on LTA- and FAU-type zeolites, at 77 K, 298 K, and 0.1-10 bar by thoroughly analyzing results of adsorption capacity experiments and molecular simulations. In the Grand Canonical Monte Carlo (GCMC) simulations, the force field causing a molecular dipole of H2 and the polarization force field of N2 are first applied. The accuracy of the force field was experimentally verified. The findings indicate that N2 and H2 loading on Ca-FAU (Ca-LTA) are higher than Na-FAU (Na-LTA). On NaX at 77 K, the highest adsorption selectivity (N2/H2) is observed; on NaA at 298 K, it is the opposite. The GCMC data findings demonstrate that H2 and N2 have remarkably similar adsorption sites, with framework oxygen atoms and non-framework cations serving as the main adsorption sites for adsorbate molecules. Furthermore, the rate at which H2 diffuses is higher than that of N2. The study of redistribution charge before and after adsorption demonstrated that N2 has a greater affinity for the framework oxygen atoms than H2. This study provides a molecular theoretical foundation for the adsorption behavior of H2-N2 mixture in zeolites.

Two‐dimensional ammonia‐linked COF structures with different substituents for the adsorption and separation of sulfur hexafluoride: A theoretical study

AbstractAs one of the most potent greenhouse gases, SF6 has a significant economic and environmental impact on the purification and recovery of exhaust gases from the semiconductor industry. The adsorption and separation performance of SF6 on a two‐dimensional covalent organic framework TAT‐COFs‐1‐AB with different functional groups (SO3H, Et, NH2, OMe, OH, H) was investigated by using grand canonical Monte Carlo (GCMC) simulations and density functional theory (DFT) calculations. The results show that the adsorption at low pressure depends on the interactions between the SF6 and COF frameworks, while at high pressure it is mainly affected by the porosity. The highest adsorption capacity of 8.44 mmol/g (298 K, 100 kPa) is exhibited by TAT‐COF‐1‐AB‐H, which has the highest porosity. Chemical functionalization was found to be effective in enhancing the SF6/N2 selectivity. Among all the functionalized COFs, TAT‐COF‐1‐AB‐NH2, with the highest specific surface area and strong heat of adsorption, showed the highest selectivity. The simulation of self‐diffusion also shows consistent results with the GCMC simulation. The findings highlight that the adsorption capacity is influenced by substituent and porosity, with SF6 showing a consistent preference for adsorption at hollow sites, as evidenced by binding energy and charge transfer analyses.

Efficient CO2 capture over N2 in flexible MOFs: Pressure driven breathing effect

Developing efficient CO2 adsorbents is imperative to mitigate excessive CO2 emission. This study employs density functional theory (DFT), Molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations to investigate CO2 capture performance in x-pcu-n via pressure-driven breathing effect at 195 K. The breathing effect is influenced by the ligand length and predominantly achieved through ligand twisting under 20–40 kPa. Longer ligands facilitate greater breathing effect, expanding dimensions by 1.04–1.24 times, thereby enhancing available space and exposing additional adsorption sites for selective CO2 uptake. The resulting capacities are measured at 10.48, 9.44, 9.30, and 5.23mmol/g, with CO2 over N2 selectivity of 1714.44, 1368.84, 1784.15, and 1224.59, respectively, in x-pcu-n (n = 4, 3, 2, and 1) at 100 kPa. This study elucidates the pressure-driven breathing effect and their applicability in CO2 capture and separation processes, offering theoretical insights for the development of efficient CO2 adsorption materials utilizing pressure-driven flexible MOFs.

Computational prediction of MOFs with the potential to improve the efficiency of industrial CO2 capture

Capturing and storing carbon dioxide produced during industrial production operations has become a global focus in terms of energy conservation and emission reduction, especially for high-emission sources such as coal-fired power plants. In this study, the high-throughput Grand Canonical Monte Carlo (HT-GCMC) simulation method was used to assess the performance of 4,188 MOFs that were carefully selected from a comprehensive pool of 10,143 CoRE-MOFs using specific criteria. Exploratory data analysis for the population demonstratedthe effect of structural properties and isosteric enthalpy on MOFs’ adsorption performance. 90 MOFs were identified as superior adsorbents that show a strong adsorption performance when screening based on four filter criteria considered important for improving industrial economic efficiency. As the desorption pressure was increased, numerous MOFs maintained their potential and met the four screening conditions. This implies that there is room to increase the desorption pressure, which suggests a potential energy saving in practical applications. HT-GCMC was applied to calculate the adsorption properties of the 90 potential MOFs using various industrial CO2 concentration levels and showed the versatility of these MOFs for use in various industrial CO2 separation schemes. In addition, the adsorption mechanism of potential MOFs was analyzed, revealing specific numerical ranges for Qst and structural characteristics that correlate with their performance. Character analysis of 90 potential MOFs revealed that the elements O, N, Zn, and Cu have the highest content; C-O, Cu-O, C-N, and Cu-N are the bonded atom pairs most commonly seen in these 90 potential MOFs.

Constructing local nanomolecular trap in a scalable, low-cost, and ultramicroporous metal–organic framework for efficient capture of greenhouse gases SF6 and CO2

The capture of sulfur hexafluoride (SF6) and carbon dioxide (CO2) is an important but challenging task for reducing greenhouse gas emission and thereby diminishing negative impacts of global climate change. Herein, we integrated local nanomolecular traps into an inexpensive cobalt-based metal–organic framework (MOF, namely GNU-3) with suitable pore sizes and functional pore surfaces for capturing greenhouse gases. Activated GNU-3a showed good adsorption and separation properties for SF6 and CO2. Especially for SF6, GNU-3a displayed the high SF6/N2 (10:90, v/v) selectivity of 317.6 and SF6 uptake capacity of 2.63mmol/g at 298 K and 1.0 bar. Grand canonical Monte Carlo simulations and first-principles dispersion-corrected density functional theory calculations identified that gas molecules were favorably trapped in polyaromatic ring functionalized channel centers and nanomolecular traps of pore walls by the strong hydrogen bond interactions. Excellent breakthrough results recommend practical separating properties of GNU-3a for binary SF6/N2 and CO2/N2 mixtures, and ternary SF6/CO2/N2 mixtures. Moreover, benefitting from superior features of cheap raw materials and large-scale synthesis, GNU-3 is expected to be applied to practical industrial scenarios. This work may provide insights into constructing prospectively industrial porous MOF adsorbents with optimal pore structures for greenhouse gas capture.

Highly efficient separation of CO2/N2 and CO2/CH4 via metal-ion regulation in ultra-microporous metal-organic frameworks

Efficient separation of CO2 from CH4 and N2 is crucial for industrial processes. This study presents a novel approach to enhance CO2/N2 and CO2/CH4 separation using metal-ion regulation in ultra-microporous metal–organic frameworks (MOFs). Specifically, we synthesized ZSTU-8-M (M=Cd, Zn) by coordinating norfloxacin ligands with different metal ions, achieving precise modulation of the pore structure. Ideal adsorption solution theory (IAST) calculations demonstrated that ZSTU-8-Cd exhibited superior selectivity for CO2/N2 (952) and CO2/CH4 (369) mixtures compared to ZSTU-8-Zn. Grand canonical Monte Carlo (GCMC) simulations and in situ single-crystal X-ray diffraction (SCXRD) confirmed the presence of specific CO2 binding sites within the pore channels. The CO2 molecule shows a unique strong adsorption mechanism of hydrogen bonding sites in this structure, and thus achieves high adsorption capacity at low pressure. Dynamic breakthrough experiments further validated the practical separation efficiency of ZSTU-8-Cd, with high retention times and saturated adsorption capacities for CO2. These findings highlight the ability of metal-ion modulation to achieve simultaneous improvement in adsorption capacity and selectivity, demonstrating the potential of MOFs for advanced gas separation applications.

Ultramicroporous metal-organic framework for efficient carbon dioxide capture from flue gas and natural gas

Carbon dioxide capture from flue gas (CO2/N2) and natural gas (CO2/CH4) is a challenging and cost-effective task. In this paper, ultramicroporous metal-organic frameworks (MOFs) (Co-norf and Ni-norf) are synthesized to realize the efficient separation of CO2/N2 and CO2/CH4 by metal ion regulation. The Ideal Adsorption Solution Theory (IAST) was calculated to evaluate the adsorption selectivity of activated Co-norf and Ni-norf for CO2/N2 (v/v = 15/85) mixtures and CO2/CH4 mixtures. The CO2/N2 selectivity of Co-norf and Ni-norf at 100 kPa was 734 and 96, respectively, which corresponds to an almost 7.6-fold increase by metal ion modulation. The specific binding sites of CO2 molecules within the pore channels were obtained by grand canonical Monte Carlo simulation (GCMC). Dynamic breakthrough experiments respond to the actual separation in systems simulating flue gas and natural gas, where the higher saturation adsorption and longer retention time proved that Co-norf is an ideal material for CO2 capture and separation. The present work provides a feasible approach for the application of MOF in gas separation.

Prediction of hydrogen storage in metal-organic frameworks using CatBoost-based approach

This study determined the machine-learning (ML) models for the discovery of efficient metal-organic framework (MOF) materials to improve hydrogen storage. We selected a sample of 5047 MOFs from the CoRE MOFs database and employed grand canonical Monte Carlo simulation results from the Hydrogen Materials Advanced Research Consortium (HyMARC) data center to evaluate the useable gravimetric (UG) capacities and useable volumetric (UV) capacities of these materials. ML models were employed to analyze the data. Seven key features were focused upon density, gravimetric surface area, volumetric surface area, void fraction (VF), pore volume (PV), largest cavity diameter, and pore-limiting diameter, and used to predict the UG and UV. The CatBoost model provided the most accurate predictions. In addition, SHapley Additive exPlanations analysis based on the CatBoost model revealed that the PV and VF significantly affected the hydrogen storage performance. A comprehensive analysis confirmed that the CatBoost model exhibited the highest prediction accuracy and identified specific combinations of structural features that significantly improved the hydrogen storage efficiency of the MOFs.

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.

Interpenetrated In(III)-MOF with Multiple Recognition Sites for Single-Step Ethylene Purification.

An interpenetrated indium(III) metal-organic framework (MOF), NTUniv-73, with a rarely reported tetrameric indium cluster is developed for streamlining ethylene purification from C2 gases. At 298 K, the adsorption capacities exhibited a complete reversal sequence of C2H6 > C2H2 > C2H4. Grand canonical Monte Carlo simulation indicated that the corners in a octahedral cage facilitated the C2H2/C2H4 separation, while the pocket-like aperture situated between adjacent octahedral cages allows for full contact of C2H6. Breakthrough experiments illustrated that NTUniv-73 could yield pure C2H4 in a single step with a productivity of 0.42 mmol g-1.

Uncovering optimal carbon and boron nitride nanotube geometries for methane and hydrogen release

We screened 1651 carbon and boron nitride (BN) nanotubes to investigate methane release at 298 K and hydrogen release at 77 K through grand canonical ensemble Monte Carlo (GCMC) simulations. The effects of nanotube radius, density, and van der Waals spacing on the release quantities of these gases were explored. Our research shows that CH4 release in C(40,40) and BN(40,40) nanotubes reaches a high of 0.15 g/g, below the DOE's 0.5 g/g target. Similarly, the best nanotubes for volumetric release, C(21,9) and BN(18,18), peak at 175 cm³/cm³, below the DOE target of 330 cm³/cm³. This suggests that internal adsorption within isolated nanotubes is insufficient to meet DOE targets, highlighting the need for optimization of inter-tube van der Waals spacing. For H2, C(40,39) and BN(40,40) nanotubes are optimal for weight release, achieving up to 12.19% at a pressure of 8 MPa. This surpasses the 2025 DOE benchmark of 5.5 wt%. Meanwhile, C(28,7) and BN(24,24) nanotubes are most suitable for volumetric release. The C(28,7) nanotube, recommended for H2 storage, reaches a volumetric release quantity close to the DOE target of 0.04 kg/L at a van der Waals spacing of 1 nm. At pressures exceeding 2 MPa, the weight adsorption outside nanotubes accounts for 40–55% of the total, underscoring the pivotal role of extra-tube adsorption in gas storage capacity for both CH4 and H2. The results provide a foundation for the design of nanotube-based materials for efficient gas storage and release, with implications for clean energy applications.

Improving Stability, Crystallinity, and Photo‐Responsiveness of Supramolecular Frameworks by Surface Polymerization

AbstractMetal–organic cage‐based photo‐responsive supramolecular frameworks (PSMFs) with permanent porosity have gained attention for their modular properties, controllable functionality, and light‐induced reversible responsiveness. However, their high porosity and photo‐responsive efficiency are often compromised due to poor structural stability upon solvent removal, limiting their potential applications. Here, a solution to overcome this challenge by employing a surface polymerization strategy using isophorone diisocyanate (IDI) to stabilize PSMF (PCC‐20t) is presented. This approach results in the composite of PCC‐20t@PolyIDI, which preserves crystallinity and permanent high‐porosity while avoiding structural collapse commonly observed in highly porous supramolecular frameworks. Moreover, compared to activated PCC‐20t, PCC‐20t@PolyIDI exhibits an 18.6‐fold increase in specific surface area. Remarkably, the structural variability of PCC‐20t@PolyIDI can be observed in the photo‐regulation behavior of CO2 capacity under the irradiation of vis‐ and UV‐light, showing a 27.9% change in adsorption amount for CO2 which is significantly higher than that of the activated PCC‐20t with 7.0% for CO2. Grand Canonical Monte Carlo simulations demonstrate the light‐regulated adsorption performance is attributed to the configuration transformation of azobenzene from trans‐ to buckling state. The findings may pave the way for stabilizing high‐porosity materials to simultaneously meet demands for high‐porosity and photo‐responsive efficiency.

Electrostatically driven kinetic inverse CO2/C2H2 separation in LTA-type zeolites

The identical molecular size and similar physical properties of carbon dioxide (CO2) and acetylene (C2H2) make their adsorptive separation extremely challenging to achieve with most adsorbents. Reports on the separation of CO2 and C2H2 mixtures by zeolites are even rarer with the mechanism of adsorptive separation requiring further exploration. In this paper, we report that ion modulation of zeolite 5A promotes the difference in kinetic diffusion of CO2 and C2H2, realizing the inverse separation of zeolite from selective adsorption of C2H2 to selective adsorption of CO2. Creating a compact pore space restricting the orientation of gas molecules enables charge recognition. The positive electrostatic potential at the pore openings was utilized to hinder the diffusion of C2H2 between the cages while ensuring the transfer of CO2, increasing their diffusion differences in pore channels and leading to the CO2/C2H2 kinetic selectivity of 31.97. Grand canonical Monte Carlo (GCMC) simulation demonstrates that the CO2 distribution in K-5A-β is significantly higher than that of C2H2. Dynamic breakthrough experiments verify the excellent performance of material in practical CO2/C2H2 separation, for CO2/C2H2 (50/50 and 1/99, V/V) mixtures can be separated in one step, thus directly generating high purity C2H2 (> 99.95%), which provides a promising thought for the zeolite-based separation of CO2 and C2H2.

Direct Ethylene Purification from a Four-Component Gas Mixture by a Microporous MOF with Aromatic Pore Surface and Carboxylates.

The single-step purification of ethylene (C2H4) from a mixture of carbon dioxide (CO2), acetylene (C2H2), ethylene (C2H4), and ethane (C2H6) was achieved through MOF Compound-1, where the aromatic pore surface and carboxylates selectively recognized C2H6 and CO2, respectively, resulting in a reversal of the adsorption orders for both gases (C2H6 > C2H4 and CO2 > C2H4). Breakthrough testing verified that the C2H4 purification ability could be enhanced 2.6 times after adding impure CO2. Grand Canonical Monte Carlo (GCMC) simulations demonstrate that there are interactions between CO2 and C2H6 molecules as well as between CO2 molecules themselves. These interactions contribute to the enhancement of the C2H4 purification ability upon the addition of CO2 and the increased adsorption of CO2.

Exploring Methane Storage Capacities of M2(BDC)2(DABCO) Sorbents: A Multiscale Computational Study

A promising solution for efficient methane (CH4) storage and transport is a metal–organic framework (MOF)-based sorbent. Hence, searching for potential MOFs like M2(BDC)2(DABCO) to enhance the CH4 storage capacity in both gravimetric and volumetric uptakes is essential. Herein, we systematically elucidate the adsorption of CH4 in M2(BDC)2(DABCO) or M(DABCO) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn) MOFs using multiscale simulations that combined grand canonical Monte Carlo simulation with van der Waals density functional (vdW-DF) calculation. We find that, in the M(DABCO) series, Mg(DABCO) has the highest total CH4 adsorption capacities, with mtot= 231.39 mg/g at 298 K, for gravimetric uptake, and Vtot= 231.43 cc(STP)/cc, for volumetric uptake. The effects of temperature, pressure, and metal substitution on enhancing CH4 storage are evaluated, and we predict that the volumetric CH4 storage capacity on M(DABCO) could meet the DOE target at temperatures of ca. 238 K–268 K and pressures of 35–100 bar. The interactions between CH4 and M(DABCO) are dominated by the vdW interactions, as shown by the vdW-DF calculations. The Mg, Mn, Fe, Co, and Ni substitutions in M(DABCO) result in a stronger interaction and thus, a higher CH4 storage capacity, at higher pressures for Mg, Mn, Ni, and Co and at lower pressures for Fe. This work may provide guidance for the rational design of CH4 storage in M2(BDC)2(DABCO) MOFs.

Data-driven discovery of novel metal organic frameworks with superior ammonia adsorption capacity

Ammonia (NH3) has been a subject of great interest due to its important roles in diverse technological applications. However, high toxicity and corrosiveness of NH3 has made it an important task to develop an efficient carrier to safely capture NH3 with high capacity. Here, we employ a machine learning (ML) model to discover high-performance metal organic frameworks (MOFs) that will work as efficient NH3 carriers. By constructing databases at two distinct conditions, adsorption and desorption, through Grand Canonical Monte Carlo (GCMC) simulations to train ML models, we identify eight novel MOFs as potentially efficient NH3 carriers through screening the large-scale MOF databases with the trained models and GCMC verification. The identified MOFs exhibit the average NH3 working capacity exceeding 1100 mg/g, and subsequent molecular dynamics simulations demonstrate mechanical stability of the predicted MOFs. Moreover, analyses of the diffusion mechanism within the proposed MOFs underscore the strong dependence of NH₃ gas diffusivity on the structural details of the materials.

Insight on molecular interactions in shrinkage of Na-montmorillonite clay by molecular dynamics simulation

Expansive soils are known to be hazardous materials for infrastructure due to their high shrinking or swelling potential. Understanding the shrinking factors of expansive soils such as montmorillonite (MMT) is essential for predicting their mechanical properties. The interactions between the components of Na-MMT clays, e.g., MMT layer–layer (LL), layer–cation (LC), layer–water (LW) and water–cation (WC), are responsible for its shrinking behavior. In this study, molecular dynamics simulation and grand canonical Monte Carlo simulations are used to investigate the interaction energy evolution in the layered structure of Na-MMT for the shrinkage mechanisms analysis of clay. The results of simulation indicate that the magnitude of the interaction energy contributed by the interlayer cations dehydration is the driving force of the interlayer shrinkage. Furthermore, in the hydrated state, with one water layer, two water layers and three water layers, the attractive interactions between WC and LW, maintain the stability of the clay layers. However, at the dry state, the interaction energy between layers and cations appears to be the most essential component in holding the stacked layers together, which provides structural stability to the clay sheets. Finally, the study reveals that intermolecular interactions contribute to the mechanical properties of clays such as cohesive and elastic properties.

Sequence dependence of critical properties for two-letter chains.

Histogram-reweighting grand canonical Monte Carlo simulations are used to obtain the critical properties of lattice chains composed of solvophilic and solvophobic monomers. The model is a modification of one proposed by Larson et al. [J. Chem. Phys. 83, 2411 (1985)], lowering the "contrast" between beads of different types to prevent aggregation into finite-size micelles that would mask true phase separation between bulk high- and low-density phases. Oligomeric chains of lengths between 5 and 24 beads are studied. Mixed-field finite-size scaling methods are used to obtain the critical properties with typical relative accuracies of better than 10-4 for the critical temperature and 10-3 for the critical volume fraction. Diblock chains are found to have lower critical temperatures and volume fractions relative to the corresponding homopolymers. The addition of solvophilic blocks of increasing length to a fixed-length solvophobic segment results in a decrease of both the critical temperature and the critical volume fraction, with an eventual slow asymptotic approach to the long-chain limiting behavior. Moving a single solvophobic or solvophilic bead along a chain leads to a minimum or maximum in the critical temperature, with no change in the critical volume fraction. Chains of identical length and composition have a significant spread in their critical properties, depending on their precise sequence. The present study has implications for understanding biomolecular phase separation and for developing design rules for synthetic polymers with specific phase separation properties. It also provides data potentially useful for the further development of theoretical models for polymer and surfactant phase behavior.

Microwave-synthesized heteroaromatic porous organic polymers for CO2 capture and hydrogen storage

In this paper, three porous organic polymers (POPs) were synthesized by microwave-assisted Friedel-Crafts polymerization reaction of 1,3,5-tris(2-thienyl)benzene (TTB) with furan (HAF), thiophene (HAT), and pyrrole (HAP) in the presence of dimethoxymethane using anhydrous iron (III) chloride as a catalyst. The polymers displayed inherent porosity, with BET surface areas ranging from 528 to 634 m2/g. These polymers exhibited high CO2 adsorption capacity, with values of 2.61, 2.17, and 2.37 mmol/g at 273 K and 1 atm, as well as strong affinity, with Qst values of 43–48 kJ/mol. The polymers showed hydrogen storage of 3.3–5.3 mmol/g (0.66–1.06 wt%) at 77 K, and 1 atm. The polymers showed Initial slope selectivity for CO2/N2: 34–61 at 273 K and 1 atm, and 23–57 at 298 K and 1 atm. Whereas, the polymers showed initial slope selectivity for CO2/CH4: 5–9 at 273 K and 4–7 at 298 K and 1 atm. Besides, the HAP at 273 K and HAF at 298 K showed highest IAST selectivity values of 231.18 and 257.49, respectively. Grand Canonical Monte Carlo (GCMC) simulations revealed that the polymers exhibit matching electronic properties with CO2 molecules and achieve excellent selectivity in accordance with the hard-soft acid-base (HSAB) theory. These findings demonstrate the potential of these polymers for CO2 capture and clean energy applications.

Computational design of novel highly connected COFs for CH4/H2 adsorption and separation

Ten new highly connected cubic boronitrate (-B4N4O12-) base covalent organic frameworks (BN-COFs) were designed in the lta and aco topologies. These structures were optimized and characterized computationally using density functional theory (DFT) and molecular mechanics methods. The structural characterization reflects that these BN-COFs possess the appropriate structural parameters for CH4/H2 adsorption and separation, such as low density (0.52–1.28 g·cm−3), high pore porosity (22 %-72 %), appropriate pore limiting diameter (PLD, 2.45–6.71 Å) and the largest cavity diameter (LCD, 3.21–19.96 Å), large pore volume (0.15–1.37 cm3·g−1) and accessible surface area (332–3974 cm2·g−1). Grand canonical Monte Carlo (GCMC) simulations were conducted to investigated the adsorption and separation properties of CH4 and H2 in ten BN-COFs. The results indicate that the uptake capacity of methane and hydrogen in BN-COF-5, −9 and −10 has exceeded the targets set by the U.S. Department of Energy (DOE). Furthermore, the CH4/H2 selectivity of ten BN-COFs is comparable to that of typical porous materials. The outstanding CH4/H2 adsorption and separation properties of these BN-COFs can provide some references and inspirations for researchers to develop high-performance porous adsorbents in experimental studies.