Molecular simulations are an important tool for the study of adsorption of hydrocarbons in nanoporous materials such as zeolites. The heat of adsorption is an important thermodynamic quantity that can be measured both in experiments and molecular simulations, and therefore it is often used to investigate the quality of a force field for a certain guest-host (g - h) system. In molecular simulations, the heat of adsorption in zeolites is often computed using either of the following methods: (1) using the Clausius-Clapeyron equation, which requires the partial derivative of the pressure with respect to temperature at constant loading, (2) using the energy difference between the host with and without a single guest molecule present, and (3) from energy/particle fluctuations in the grand-canonical ensemble. To calculate the heat of adsorption from experiments (besides direct calorimetry), only the first method is usually applicable. Although the computation of the heat of adsorption is straightforward for all-silica zeolites, severe difficulties arise when applying the conventional methods to systems with nonframework cations present. The reason for this is that these nonframework cations have very strong Coulombic interactions with the zeolite. We will present an alternative method based on biased interactions of guest molecules that suffers less from these difficulties. This method requires only a single simulation of the host structure. In addition, we will review some of the other important issues concerning the handling of these strong Coulombic interactions in simulating the adsorption of guest molecules. It turns out that the recently proposed Wolf method ( J. Chem. Phys. 1999, 110 , 8254 ) performs poorly for zeolites as a large cutoff radius is needed for convergence.

The adsorption properties of CO 2 , N 2 and CH 4 in all-silica zeolites were studied using molecular simulations. Adsorption isotherms for single components in MFI were both measured and computed showing good agreement. In addition simulations in other all silica structures were performed for a wide range of pressures and temperatures and for single components as well as binary and ternary mixtures with varying bulk compositions. The adsorption selectivity was analyzed for mixtures with bulk composition of 50:50 CO 2 /CH 4 , 50:50 CO 2 /N 2 , 10:90 CO 2 /N 2 and 5:90:5 CO 2 /N 2 /CH 4 in MFI, MOR, ISV, ITE, CHA and DDR showing high selectivity of adsorption of CO 2 over N 2 and CH 4 that varies with the type of crystal and with the mixture bulk composition.

ZIF-8 is a zeolitic imidazolate framework with very good thermal and chemical stability that opens up many applications that are not feasible by other metal-organic frameowrks (MOFs) and zeolites. Several works report the adsorption properties of ZIF-8 for strategic gases. However, despite the vast experimental corpus of data reported, there seems yet to be a dearth in the understanding of the gas adsorption properties. In this work we provide insights at a molecular level on the mechanisms governing the ZIF-8 structural deformation during molecular adsorption. We demonstrate that the ZIF-8 structural deformation during the adsorption of different molecules at cryogenic temperature goes beyond the gas-induced rotation of the imidazolate linkers. We combine experimental and simulation studies to demonstrate that this deformation is governed by the polarizability and molecular size and shape of the gases, and that the stepped adsorption behavior is defined by the packing arrangement of the guest inside the host.

Mixed matrix membranes (MMMs) composed of metal organic framework (MOF) fillers embedded in a polymeric matrix represent a promising alternative for CO2 removal from natural gas and biogas. Here, MMMs based on NH2‐MIL‐53(Al) MOF and polyimide are successfully synthesized with MOF loadings up to 25 wt% and different thicknesses. At 308 K and ΔP = 3 bar, the incorporation of the MOF filler enhances CO2 permeability with respect to membranes based on the neat polymer, while preserving the relatively high separation factor. The rate of solvent evaporation after membrane casting proves key for the final configuration and dispersion of the MOF in the membrane. Fast solvent removal favours the contraction of the MOF structure to its narrow pore framework configuration, resulting in enhanced separation factor and, particularly, CO2 permeability. The study reveals an excellent filler‐polymer contact, with ca. 0.11% void volume fraction, for membranes based on the amino‐functionalized MOF, even at high filler loadings (25 wt%). By providing precise and quantitative insight into key structural features at the nanoscale range, the approach provides feedback to the membrane casting process and therefore it represents an important advancement towards the rational design of mixed matrix membranes with enhanced structural features and separation performance.

We use Monte Carlo simulations to study the adsorption and separation of the natural gas components in IRMOF-1 and Cu-BTC metal-organic frameworks. We computed the adsorption isotherms of pure components, binary, and five-component mixtures analyzing the siting of the molecules in the structure for the different loadings. The bulk compositions studied for the mixtures were 50 : 50 and 90 : 10 for CH4-CO2, 90 : 10 for N2-CO2, and 95 : 2.0 : 1.5 : 1.0 : 0.5 for the CH4-C2H6-N2-CO2-C3H8 mixture. We choose this composition because it is similar to an average sample of natural gas. Our simulations show that CO2 is preferentially adsorbed over propane, ethane, methane and N2 in the complete pressure range under study. Longer alkanes are favored over shorter alkanes and the lowest adsorption corresponds to N2. Though IRMOF-1 has a significantly higher adsorption capacity than Cu-BTC, the adsorption selectivity of CO2 over CH4 and N2 is found to be higher in the latter, proving that the separation efficiency is largely affected by the shape, the atomic composition and the type of linkers of the structure.

The adsorption of several quadrupolar and nonpolar gases on the Metal Organic Framework Cu-BTC has been studied by combining experimental measurements and Monte Carlo simulations. Four main adsorption sites for this structure have been identified: site I close to the copper atoms, site I' in the bigger cavities, site II located in the small octahedral cages, and site III at the windows of the four open faces of the octahedral cage. Our simulations identify the octahedral cages (sites II and III) and the big cages (site I') as the preferred positions for adsorption, while site I, near the copper atoms, remains empty over the entire range of pressures analyzed due to its reduced accessibility. The occupation of the different sites for ethane and propane in Cu-BTC proceeds similarly as for methane, and shows small differences for O2 and N2 that can be attributed to the quadrupole moment of these molecules. Site II is filled predominantly for methane (the nonpolar molecule), whereas for N2, the occupation of II and I' can be considered almost equivalent. The molecular sitting for O2 shows an intermediate behavior between those observed for methane and for N2. The differences between simulated and experimental data at elevated temperatures for propane are tentatively attributed to a reversible change in the lattice parameters of Cu-BTC by dehydration and by temperature, blocking the accessibility to site III and reducing that to site I'. Adsorption parameters of the investigated molecules have been determined from the simulations.

Low-coverage adsorption properties of the metal-organic framework MIL-47 were determined by a combined experimental and simulation study. Henry constants and low coverage adsorption enthalpies of C5-C8 linear and branched alkanes, cyclohexane and benzene were measured from 120 to 240 degrees C using pulse gas chromatography. An adapted force field for linear and branched alkanes in MIL-47 was used to compute the adsorption properties of those molecules. A new set of charges was developed for simulations with benzene in MIL-47. The adsorption enthalpy of linear alkanes increases with about 7.6 kJ mol(-1) per additional -CH2- group. Henry adsorption constants of iso-alkanes are slightly lower than those of the linear chains but the MIL-47 framework is not imposing steric constraints on the branched chains. Benzene and cyclohexane are adsorbed less strongly than n-hexane as they have less hydrogen atoms. For the studied non-polar molecules, the adsorption energies are dominated by van der Waals interactions and benzene adsorption is additionally influenced by Coulombic interactions. The simulated tendencies are in good agreement with the experiments.

Recent adsorption isotherms of n-alkanes on Ca,Na-LTA-type zeolite afford development of a force field describing the interactions between calcium and n-alkanes in configurational-bias Monte Carlo simulations. The force field of Calero et al. (J. Am. Chem. Soc. 2004, 126, 11377-11386) is able to accurately describe the adsorption properties of linear alkanes in the sodium form of FAU-type zeolites. Here, we extend upon this type of force field by including calcium-type ions. The force field was fitted to reproduce the calcium and sodium cations positions on LTA 5A and the experimental adsorption properties of n-alkanes over all range of temperatures and pressures. This opens up a vast amount of experimental data on LTA 5A, both on adsorption and diffusion. Furthermore, evaluation of half a century of reported n-alkane adsorption data on LTA-type zeolites indicates that there are many inconsistencies between the various data sets, possibly as a result of (i) undisclosed calcium and sodium contents, (ii) less than perfect drying of the hygroscopic zeolite, and (iii) coadsorption of contaminants such as vacuum grease. Having obtained our force field, and confirmed its reliability on predictions outside the calibration set, we apply the force field on two "open" problems: (a) the heats of adsorption and Henry coefficient as a function of chain length and (b) the effect of cations in LTA-type zeolites. The molecular simulations shed new light on previous experimental findings, and we provide rationalizations on the molecular level that can be generalized to the class of cage/window-type nanoporous materials.