CH4 Adsorption Research Articles

Efficient and selective CO2 capture at low concentration from CH4 or N2 using Zn-MOF@AFP composite

The synthesis of structured CO2 adsorbents with high separation selectivity, strong stability, and low cost to meet industrial needs is very challenging. Here, we synthesized an ultra-stable Zn-MOF (Zn2(3-amion-1,2,4-triazolate)2(oxalate), Zn2(Atz)2Ox), and adopted an efficient in-situ growth strategy to produce millimeter-sized spherical Zn2(Atz)2Ox@AFP (Amino-Functionalization Poly(acrylates), AFP) composite. Due to the heterogeneous crystallization induced by the nanoscale crystal seeds and the confined space of AFP, the three-dimensional (3D) Zn2(Atz)2Ox bulk crystals transformed into 2D nanosheets with higher CO2 adsorption efficiency and faster kinetics. Zn2(Atz)2Ox@AFP has a high affinity for CO2 (2.05 mmol g−1 at 0.05 bar and 313 K) while exhibiting an inhibitory effect for N2 (only 0.051 mmol g−1 at 1.0 bar and 313 K), leading to an excellent ideal adsorbed solution theory (IAST) selectivity (2990 for CO2/N2 (5/95, v/v)). Interestingly, Zn2(Atz)2Ox@AFP exhibits a unique gating effect on CH4 adsorption, which further extends its application range to natural gas purification. Dynamic breakthrough experiments confirmed that Zn2(Atz)2Ox@AFP can selectively capture CO2 in the simulated CO2/N2 (5/95) and CO2/CH4 (5/95) mixed gases.

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.

Unveiling methane sensing mechanisms of graphene and its derivatives

Natural gas has become one primary energy source. However, using natural gas imposes enormous challenges since natural gas leaks may cause catastrophic damage to the environment and human life. As the main component of natural gas, methane (CH4) is a type of greenhouse gas that exacerbates global warming and has a risk of explosion in air. Developing CH4 sensing technology is crucial to detect natural gas leaks. Despite tremendous efforts in exploring gas sensing by graphene and its derivatives, the low reactivity limited the application of graphene-based materials in CH4 detection. Here, density functional theory (DFT) calculations were carried out to study graphene and its derivatives’ CH4 adsorption energy, sensitivity, and selectivity. Graphene derivatives with hydroxyl groups around surface vacancies were found to be superior in CH4 sensing over other graphene derivatives. Our findings offer new design guidelines for developing CH4 sensors.

Extra-High CO2 Adsorption and Controllable C2H2/CO2 Separation Regulated by the Interlayer Stacking in Pillar-Layered Metal-Organic Frameworks.

Pillar-layered metal-organic frameworks (PLMOFs) are promising gas adsorbents due to their high designability. In this work, high CO2 storage capacity as well as controllable C2H2/CO2 separation ability are acquired by rationally manipulating the interlayer stacking in pillar-layered MOF materials. The rational construction of pillar-layered MOFs started from the 2D Ni-BTC-pyridine layer, an isomorphic structure of pioneering MOF-1 reported in 1995. The replacement of terminal pyridine groups by bridging pyrazine linkers under optimized solvothermal conditions led to three 3D PLMOFs with different stacking types between adjacent Ni-BTC layers, named PLMOF 1 (ABAB stacking), PLMOF 2 (AABB stacking), and PLMOF 3 (AAAA stacking). Regulated by the layer arrangements, CO2 and C2H2 adsorption capacities (273 K and 1 bar) of PLMOFs 1-3 vary from 173.0/153.3, 185.0/162.4, to 203.5/159.5 cm3 g-1, respectively, which surpass the values of most MOF adsorbents. Dynamic breakthrough experiments further indicate that PLMOFs 1-3 have controllable C2H2/CO2 separation performance, which can successfully overcome the C2H2/CO2 separation challenge. Specially, PLMOFs 1-3 can remove trace CO2 (3%) from the C2H2/CO2 mixture and produce high-purity ethylene (99.9%) in one step with the C2H2 productivities of 1.68, 2.45, and 3.30 mmol g-1, respectively. GCMC simulations indicate that the superior CO2 adsorption and unique C2H2/CO2 separation performance are mainly ascribed to different degrees of CO2 agglomeration in the ultramicropores of these PLMOFs.

Statistical mechanic and machine learning approach for competitive adsorption of CO2/CH4 on coals and shales for CO2-enhanced methane recovery

Understanding the adsorption behavior of CO2, CH4, and their mixture on coal at high pressures is necessary to achieve enhanced CH4 recovery and the simultaneous sequestration of CO2. The adsorption of CO2 and CH4 on dry coal is known to exhibit complex behavior as a function of temperature, pressure, and composition. In this study, a model for CO2 adsorption under supercritical conditions was proposed based on a combination of surface adsorption and dissolution in the coal matrix. However, the corresponding CH4 adsorption can only be presented by a surface mechanism. Although the theoretical model provides an idealized description of the heterogeneous nature of coal, it retains the ability to capture the qualitative features of the experimental isotherms. The results indicate reasonable adsorption on the coal surface and dissolution into the coal matrix in the model mechanisms. The model also provides binding energies, surface areas, absolute adsorption isotherms, and isotherms in terms of the fractional occupancy. Considering the complex behavior of mixture adsorption, a machine learning (ML) approach was applied to the adsorption data of various coals. The ML model was reliable for predicting the competitive adsorption of CO2 and CH4 regardless of the coal type (R2 = 0.9950 and 0.9923 for CO2 and CH4, respectively). According to the analytical results obtained from the theoretical model and the ML approach, the volatile matter content, fixed carbon content, and vitrinite reflectance of coal were determined to be important properties for predicting the competitive adsorption of CO2 and CH4 on coal.

Metal-Organic Framework Featuring Cubic Caged Structures for One-Step Ethylene Purification from Ethylene/Ethane Mixtures.

Separation of C2H6/C2H4 mixtures is of significant importance in the chemical industry but remains a challenge due to the physicochemical similarities of C2H6 and C2H4. Herein, a metal-organic framework (MOF), [Zn4(μ4-O)(PCTF)3]n (Zn-PCTF) (PCTF2-= 5-trifluoromethyl-1H-pyrazole-4-carboxylic), is provided for the removal of C2H6 from C2H6/C2H4 mixtures. Zn-PCTF displays a three-dimensional framework featuring one-dimensional pore channels with periodic bottleneck segments. The well-balanced C2H6 adsorption capacity (79.0 cm3 g-1 at 298 K) and C2H6/C2H4 selectivity (1.8) for Zn-PCTF under ambient conditions boost Zn-PCTF with highly promising potentials for efficient purification of C2H4 from C2H6/C2H4 mixtures, which is verified by the dynamic column breakthrough experiments. The well-matched caged pores and suitable pore chemistry (particularly the presence of abundant Lewis base sites (N, O, and F) on the pore surfaces) for C2H6 account for the high-performance C2H6/C2H4 separation of Zn-PCTF unveiled by computational simulations.

Evaluation of methane adsorption isotherms at ambient temperature on carbon materials from NLDFT pore size analysis derived from standard N2 and CO2 adsorption isotherms

In this paper, we attempt to estimate CH4 adsorption on carbon materials based on the pore size distribution (PSD) characteristics evaluated from standard nitrogen and carbon dioxide adsorption isotherms using the nonlocal density functional theory (2D-NLDFT), or more precisely, its two-dimensional version (2D-NLDFT). The PSDs of the carbons were calculated by the simultaneous fit of the NLDFT models to the corresponding N2 and CO2 adsorption data. This method is referred to in the literature as the dual gas analysis method which is implemented in SAIEUS software. Essential features of carbon PSDs affecting the shapes of methane adsorption isotherms measured at ambient temperature were identified as related to micro and mesopores carbon structure. We discuss how different micro and mesopore size ranges contribute to methane adsorption isotherms in the low and higher-pressure ranges. The results of the present study may serve as guidance for selecting and designing suitable carbon materials for practical applications such as PSA recovery of CH4 from its mixtures or for methane storage.

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.

Immobilization of Lewis Basic Sites into a Quasi‐Molecular‐Sieving Metal–Organic Framework for Enhanced C3H6/C3H8 Separation

AbstractControlling gas sorption through pore engineering is indispensable in molecular recognition and separation processes. The challenge lies in developing high‐efficiency adsorbents for C3H6/C3H8 separation, specifically enhancing the affinity toward C3H6 for high selectivity while maintaining a large gas uptake to obtain high separation efficiency. Herein, this problem can be addressed by controlling host‐guest interactions using Lewis basic sites modulation. A precise steric design of channel pores using an amino group as additional interacting sites enables the synergetic increase in C3H6 adsorption while suppressing the C3H8 adsorption, resulting in a quasi‐molecular‐sieving effect. Among them, TYUT‐23 has a perfect pore size that fits minimum cross‐sectional dimensions of C3H6, affording exceptional binding affinity for the C3H6 molecule. It adsorbs a large amount of C3H6 (2.5 mmol g−1) and concurrently exhibits both remarkably high IAST selectivity (71) under ambient conditions. Equimolar C3H6/C3H8 breakthrough experiments also prove the prominent separation performance of TYUT‐23 for the production of high‐purity C3H6. The C3H6 adsorption/separation mechanism has been investigated using C3H6‐loaded single‐crystal structure analysis. This material demonstrates the potential of optimizing host‐C3H6 interactions using Lewis basic site modulation in industrial separations.

High-pressure gas adsorption on activated carbons from pomegranate peels biochar: A promising approach for biogas purification

Biogas is a promising bioenergy source and its composition is based on methane (55–70% vol) but contains impurities such as CO2 (30–45% vol). Various technologies are available to purify biogas and produce biomethane that can be injected into the existing natural gas network. In this work, the effectiveness of activated carbons (ACs) obtained by chemical activation from industrial food waste for CO2 removal by adsorption was investigated. ACs with better textural development were obtained at higher activation temperature and dose of the activating agent (BET surface area and total pore volume up to 1446 m2/g and 0.589 cm3/g, respectively). The adsorbents exhibited a microporous character (micropore volume up to 0.472 cm3/g). The ACs were tested in high-pressure gas adsorption tests (CO2, CH4 and H2 up to 3, 8 and 4 MPa, respectively). All of them showed high, medium and low selectivity against for the adsorption of CO2, CH4 and H2, respectively, although with different efficiencies. The adsorbent obtained under the most aggressive activation conditions (900 °C, 1:1 wt ratio) showed the greatest textural development and the maximum adsorption capacity for CO2 (at 3 MPa) and CH4 (at 8 MPa) (495 mgCO2/g and 126 mgCH4/g). Despite the porosity of the materials, all showed a very low affinity for hydrogen adsorption at 4 MPa (up to 3.71 mgH2/g). Taking the above into account, these activated carbons could be used in the purification of biogas and in the separation of CO2/H2 mixtures to produce pure H2 and obtain hydrogen-free CO2 for capture and storage.

Enhancing shale gas recovery: An interdisciplinary power-law model of hydro-mechanical-fracture dynamics

This study explores the efficiency of using carbon dioxide (CO2) to extract shale gas, highlighting its potential to enhance extraction while mitigating environmental CO2 pollution. Given the intricate microstructure of shale, CO2 injection inevitably induces deformation within the shale reservoir's internal microstructure, thereby impacting gas displacement efficiency. The organic matter (kerogen) network and fracture network in shale, serving as primary spaces for gas adsorption and migration, exhibit complex microstructural characteristics. Thus, we developed a dynamic coupled hydro-mechanics permeability model for binary gas displacement, and three novel, interdisciplinary fractal power-law parameters are proposed to represent the distribution of shale fractures, considering the adsorption–desorption strength of the kerogen network. Numerical simulations analyzed the changes in gas seepage, diffusion, shale stress, permeability, and factors influencing displacement efficiency during the CO2–EGR (enhanced gas recovery) projects. Key findings include (1) CO2 injection leads to a nonlinear increase in the number of shale fracture networks, thereby enhancing the CH4 output efficiency. (2) Compared to traditional fractal theory, the proposed power-law model is applicable to a wider range of reservoir fracture distributions and effectively characterizes the density (by α), size (by r), and complexity (by n) of the fracture network during the CO2–EGR process. (3) Changes in the proposed interdisciplinary power-law parameters significantly alter CO2 and CH4 adsorption capacities and, in turn, significantly affects displacement efficiency and shale deformation. According to calculations, these parameters have the greatest impact on the CO2–EGR process, ranging from 16.3% to 68.1%.

Comparative study on different coals from the Lorraine basin (France) by sorption isotherms, thermogravimetric analysis and breakthrough curves for CO2-ECBM recovery

The enhanced coalbed methane recovery using CO2 injection (CO2-ECBM) is widely proposed as a way of achieving the energy transition and reducing atmospheric CO2 in areas such as the Lorrain basin in France, where heavy industry is responsible for huge CO2 emissions and coal mines have been closed for more than a decade. This paper deals with the feasibility of extracting methane from the Lorraine basin using CO2-ECBM by comparing data from sorption isotherms, thermogravimetric analyses and breakthrough curves for two coal samples. One is bituminous (Box 18), from Folschviller (France) and is compared with another sub-bituminous (TH01) from La Houve (France), which is used as a reference because it was identified as a good candidate for CO2-ECBM in a previous research program. The quantities of adsorbed gases (CO2/CH4) obtained by sorption isotherms, thermogravimetry and CO2 breakthrough curves showed that Box 18 adsorbs more CO2 and CH4 than TH01 due to its higher porosity and good affinity for gases (CO2/CH4). Tόth model fits the experimental CH4 and CO2 adsorption isotherms better, reflecting the fact that the adsorption surface of the coals studied is heterogeneous. Adsorption enthalpies obtained by calorimetry indicated physisorption for gas-coal interactions, with higher values for CO2 than for CH4. Thermogravimetric analyses and breakthrough curves carried out at up to 50% relative humidity showed that the adsorption capacity of CO2 decreases with increasing temperature and the presence of water, respectively. The compilation of these experimental data explained the adsorption process of the studied coals and revealed their advantages for CO2-ECBM.

Selective adsorption of coalbed methane on multilayer defective graphene nanostructures and their Mn-modified nanostructures: A DFT study

Coalbed methane (CBM) is an unconventional natural gas with CH4 as the main component. It is found in coal seams and surrounding rocks. The development and exploitation of CBM is a promising approach to ensure the safety of coal mine production, reduce greenhouse effects, and increase clean energy resources. Based on the first-principles calculations in conjunction with a grand canonical Monte Carlo (GCMC) simulation, this paper aims to examine the effects of interlayer spacing and Mn modification on CBM and CO2 adsorption. We assess the CH4 storage performance in multilayered defective graphene nanostructures (MDGNs). Using density functional theory in conjunction with the Grimm correction method (DFT-D approach), both the adsorption energy and charge distribution between CBM components and extended line defects (ELD) are appropriately evaluated in the presence or lack of Mn modification (Mn-ELD). The GCMC simulation is implemented to investigate CH4 adsorption isotherms of MDGN and Mn-MDGN configurations at 298.15 K. The selective adsorption capabilities of MDGNs and Mn-MDGNs for CO2, N2, and CH4 are also systematically analyzed. The obtained results reveal that an Mn-MDGN configuration with an interlayer spacing of dGL=1.02 nm is effective in sequestering CO2 from CBM. In contrast, MDGN configurations with interlayer spacings of dGL=0.68 and 1.02 nm are more effective for the storage of purified CBM. In continuing, the CH4 purification mechanism in Mn-MDGNs and the CH4 storage mechanism in MDGNs are also methodically explored at the molecular level. The research work reported here can serve as a crucial guide for the future development and utilization of CBM.

New insight into CH4 adsorption mechanism in coal based on modeling analysis of different adsorption theories

Based on the principle of Gibbs excess adsorption measurement, high-pressure isothermal adsorption and desorption experiments of CH4 were performed on fractured coal samples, and CH4 adsorption phase density was obtained by the intercept method according to the experimental data. The Langmuir model, BET model, DA model, and their corrected model, the supercritical adsorption models were used for the fitting analysis of CH4 excess adsorption capacity. A hybrid model of different adsorption theories was developed based on CH4 adsorption phase density and theoretical adsorption capacity predicted by the intercept method. The transition in the occurrence pattern and control mechanism of CH4 in coal were investigated. The fitting of the Langmuir model, BET model, DA model, and their corrected models, the SBET model, the SDA model, and the SDA-L model to the CH4 excess adsorption capacity in coal shows that all multilayer adsorption theory model is not suitable for fitting the CH4 excess adsorption capacity in coal. The uncorrected Langmuir model and DA model are only suitable for fitting the CH4 excess adsorption capacity in coal in the low-pressure stage (pressure below 10 MPa). The corrected Langmuir model, the corrected DA model, the SDA model, and the SDA-L model can be used to fit the CH4 excess adsorption capacity in coal, but they show some bias in predicting the theoretical CH4 adsorption capacity and the CH4 adsorption phase density. The fitting of the three main adsorption theory models suggests that there may be simultaneous monolayer adsorption and microporous filling adsorption. The fitting results of the hybrid model based on monolayer adsorption and microporous filling adsorption theory depend on showing that with the increase of temperature, the occurrence of CH4 in coal gradually changes from mainly monolayer adsorption to mainly microporous filling adsorption, and the transformation of occurrence mode is related to temperature and the development of pores in coal.

Hydroxyl-functionalized linker endows an ultra-microporous aluminum based metal–organic framework with electronegative site for enhancing ethane/ethylene separation

Efficient purification of ethylene (C2H4) from the cracking gas containing a small amount of ethane (C2H6) by selective adsorption of C2H6 is meaningful but remains challenging. Aluminum-based metal–organic frameworks (Al-MOFs) with ultra-microporous structure show preferential adsorption of C2H6 over C2H4, relying on the existence of multiple hydrogen bonding acceptors (e.g., AlO6 polyhedra) for C2H6 molecule in the confined pores. However, most Al-MOFs exhibit limited C2H6/C2H4 selectivity (<2), which lack other strong preferential binding sites for C2H6. Here we report that a hydroxyl functionalized Al-MOF (i.e., CAU-1-OH) exhibits notably improved C2H6/C2H4 selectivity (2.13) and C2H6 uptake (3.95 mmol g−1) at 298 K and 1 bar compared to its amino-functionalized counterpart, CAU-1-NH2. Prior to experiment, theoretical calculations were performed, revealing that O atom from hydroxyl group in CAU-1-OH acts as a fairly strong hydrogen bond acceptor due to its more negative charge than N atom in CAU-1-NH2. The in-situ infrared experiment further confirmed the formation of multiple hydrogen bonds (C–H⋅⋅⋅O) between CAU-1-OH and C2H6 molecules, which plays vital role for C2H6-selective capture. The actual potential for C2H4 purification was fully demonstrated by dynamic breakthrough experiments, in which CAU-1-OH displayed excellent separative performance from C2H6/C2H4 (1/15, v/v) mixture. Moreover, the structural stability and excellent recyclability suggested and the promise for cost-effective industrial application in C2H6/C2H4 separation.

Rational design of carbon materials with tailored pore structure for efficient separation of CH4/N2 mixture

The highly-efficient separation of CH4/N2 mixture on carbon materials is significantly hindered by the inherent trade-off that exists between CH4 adsorption capacity and CH4/N2 separation selectivity. Herein, we have constructed a type of novel carbon materials (PGC-x) with well-controlled ultramicropores ranging from 0.48 to 0.57 nm for CH4/N2 separation. The Zn-based salt template was in-situ confined into the polymer framework during the co-assembly of phloroglucinol and glyoxylic acid. The subsequent evaporation of Zn at high temperature gives rise to the adjustable ultramicropore structure, effectively devoid of mesopores and macropores. Benefiting from the optimal pore size of 0.50 nm, PGC-1 demonstrated high CH4 uptake of up to 1.50 mmol/g. Meanwhile, the CH4/N2 (15/85 and 85/15, v/v) separation selectivity of PGC-1 at 298 K and 1.0 bar reached 5.8 and 6.0, respectively. Dynamic breakthrough experiments proved that PGC-1 could be used as efficient adsorbent for capturing low or high concentration of CH4 from N2. This work offers a promising design principle for optimizing porous structure of carbon materials, with the aim of minimizing the selectivity-capacity trade-off that often arises in the separation of diverse gas pairs.

Supramolecular Entanglement in a Hydrogen‐Bonded Organic Framework Enables Flexible‐Robust Porosity for Highly Efficient Purification of Natural Gas

AbstractThe development of porous materials with flexible‐robust characteristics shows some unique advantages to target high performance for gas separation, but remains a daunting challenge to achieve so far. Herein, we report a carboxyl‐based hydrogen‐bonded organic framework (ZJU‐HOF‐8a) with flexible‐robust porosity for efficient purification of natural gas. ZJU‐HOF‐8a features a four‐fold interpenetrated structure with dia topology, wherein abundant supramolecular entanglements are formed between the adjacent subnetworks through weak intermolecular hydrogen bonds. This structural configuration could not only stabilize the whole framework to establish the permanent porosity, but also enable the framework to show some flexibility due to its weak intermolecular interactions (so‐called flexible‐robust framework). The flexible‐robust porosity of ZJU‐HOF‐8a was exclusively confirmed by gas sorption isotherms and single‐crystal X‐ray diffraction studies, showing that the flexible pore pockets can be opened by C3H8 and n‐C4H10 molecules rather by C2H6 and CH4. This leads to notably higher C3H8 and n‐C4H10 uptakes with enhanced selectivities than C2H6 over CH4 under ambient conditions, affording one of the highest n‐C4H10/CH4 selectivities. The gas‐loaded single‐crystal structures coupled with theoretical simulations reveal that the loading of n‐C4H10 can induce an obvious framework expansion along with pore pocket opening to improve n‐C4H10 uptake and selectivity, while not for C2H6 adsorption. This work suggests an effective strategy of designing flexible‐robust HOFs for improving gas separation properties.

Structural Characterisation of Zeolites Derived from Lithium Extraction: Insights into Channel- and Cage-Type Frameworks

This study investigates the structural and adsorption characteristics of channel- and cage-type zeolites obtained through lithium extraction. Through XRD, FT-IR spectroscopy, and adsorption isotherm analyses, distinct adsorption behaviours of CH4 and CO2 were observed in both zeolite types. Cage-type zeolites exhibited higher adsorption capacities attributed to their structural advantages, highlighting the importance of structural framework selection in determining adsorbent efficacy. The presence of structural defects and an amorphous phase influenced adsorption behaviours, while thermodynamic data underscored the role of adsorbate properties. Kinetics studies revealed the influence of the structural framework on CH4 adsorption and CO2 adsorption kinetics. Analysis of adsorbate–adsorbent interactions demonstrated robust interactions, particularly with LPM16-Y. These findings offer insights into the potential applications of zeolites in gas adsorption processes, emphasising the importance of structural properties and adsorbate characteristics in determining adsorption performance.

Topology Reconfiguration of Anion-Pillared Metal-Organic Framework from Flexibility to Rigidity for Enhanced Acetylene Separation.

Flexible metal-organic framework (MOF) adsorbents commonly encounter limitations in removing trace impurities below gate-opening threshold pressures. Topology reconfiguration can fundamentally eliminate intrinsic structural flexibility, yet remains a formidable challenge and is rarely achieved in practical applications. Herein, a solvent-mediated approach is presented to regulate the flexible CuSnF6-dpds-sql (dpds = 4,4''-dipyridyldisulfide) with sql topology into rigid CuSnF6-dpds-cds with cds topology. Notably, the cds topology is unprecedented and first obtained in anion-pillared MOF materials. As a result, rigid CuSnF6-dpds-cds exhibits enhanced C2H2 adsorption capacity of 48.61 cm3 g-1 at 0.01bar compared to flexible CuSnF6-dpds-sql (21.06 cm3 g-1). The topology transformation also facilitates the adsorption kinetics for C2H2, exhibiting a 6.5-fold enhanced diffusion time constant (D/r2) of 1.71 × 10-3 s-1 on CuSnF6-dpds-cds than that of CuSnF6-dpds-sql (2.64 × 10-4 s-1). Multiple computational simulations reveal the structural transformations and guest-host interactions in both adsorbents. Furthermore, dynamic breakthrough experiments demonstrate that high-purity C2H4 (>99.996%) effluent with a productivity of 93.9mmol g-1 can be directly collected from C2H2/C2H4 (1/99, v/v) gas-mixture in a single CuSnF6-dpds-cds column.

Molecular simulations of the effects of CO2 and N2 injection on CH4 adsorption, coal porosity and permeability

Molecular simulations of the effects of CO2 and N2 injection on CH4 adsorption, coal porosity and permeability