Highlighting the Anti-Synergy between Adsorption and Diffusion in Cation-Exchanged Faujasite Zeolites.

Using configurational-bias Monte Carlo simulations of adsorption equilibrium and molecular dynamics simulations of guest diffusivities of CO2, CH4, N2, and O2 in FAU zeolites with varying amounts of extra-framework cations (Na+ or Li+), we demonstrate that adsorption and diffusion do not, in general, proceed hand-in-hand. Stronger adsorption often implies reduced mobility. The anti-synergy between adsorption and diffusion has consequences for the design and development of pressure-swing adsorption and membrane separation technologies for CO2 capture and N2/O2 separations.

How Reliable Is the Ideal Adsorbed Solution Theory for the Estimation of Mixture Separation Selectivities in Microporous Crystalline Adsorbents?

Microporous crystalline adsorbents such as zeolites and metal-organic frameworks (MOFs) have potential use in a wide variety of separation applications. The adsorption selectivity S ads is a key metric that quantifies the efficacy of any microporous adsorbent in mixture separations. The Ideal Adsorbed Solution Theory (IAST) is commonly used for estimating the value of S ads, with unary isotherms of the constituent guests as data inputs. There are two basic tenets underlying the development of the IAST. The first tenet mandates a homogeneous distribution of adsorbates within the pore landscape. The second tenet requires the surface area occupied by a guest molecule in the mixture to be the same as that for the corresponding pure component. Configurational-bias Monte Carlo (CBMC) simulations are employed in this article to highlight several scenarios in which the IAST fails to provide a quantitatively correct description of mixture adsorption equilibrium due to a failure to conform to either of the two tenets underpinning the IAST. For CO2 capture with cation-exchanged zeolites and MOFs with open metal sites, there is congregation of CO2 around the cations and unsaturated metal atoms, resulting in failure of the IAST due to an inhomogeneous distribution of adsorbates in the pore space. Thermodynamic non-idealities also arise due to the preferential location of CO2 molecules at the window regions of 8-ring zeolites such as DDR and CHA or within pockets of MOR and AFX zeolites. Thermodynamic non-idealities are evidenced for water/alcohol mixtures due to molecular clustering engendered by hydrogen bonding. It is also demonstrated that thermodynamic non-idealities can be strong enough to cause selectivity reversals, which are not anticipated by the IAST.

Synergistically enhance confined diffusion by continuum intersecting channels in zeolites.

In separation and catalysis applications, adsorption and diffusion are normally considered mutually exclusive. That is, rapid diffusion is generally accompanied by weak adsorption and vice versa. In this work, we analyze the anomalous loading-dependent mechanism of p-xylene diffusion in a newly developed zeolite called SCM-15. The obtained results demonstrate that the unique system of "continuum intersecting channels" (i.e., channels made of fused cavities) plays a key role in the diffusion process for the molecule-selective pathways. At low pressure, the presence of strong adsorption sites and intersections that provide space for molecule rotation facilitates the diffusion of p-xylene along the Z direction. Upon increasing the molecular uptake, the adsorbates move faster along the X direction because of the effect of continuum intersections in reducing the diffusion barriers and thus maintaining the large diffusion coefficient of the diffusing compound. This mechanism synergistically improves the diffusion in zeolites with continuum intersecting channels.

Using Molecular Simulations to Unravel the Benefits of Characterizing Mixture Permeation in Microporous Membranes in Terms of the Spreading Pressure.

The separation performance of microporous crystalline materials in membrane constructs is dictated by a combination of mixture adsorption and intracrystalline diffusion characteristics; the permeation selectivity S perm is a product of the adsorption selectivity S ads and the diffusion selectivity, S diff. The primary objective of this article is to gain fundamental insights into S ads and S diff by use of molecular simulations. We performed configurational-bias Monte Carlo (CBMC) simulations of mixture adsorption equilibrium and molecular dynamics (MD) simulations of guest self-diffusivities of a number of binary mixtures of light gaseous molecules (CO2, CH4, N2, H2, and C2H6) in a variety of microporous hosts of different pore dimensions and topologies. Irrespective of the bulk gas compositions and bulk gas fugacities, the adsorption selectivity, S ads, is found to be uniquely determined by the adsorption potential, Φ, a convenient and practical proxy for the spreading pressure π that is calculable using the ideal adsorbed solution theory for mixture adsorption equilibrium. The adsorption potential Φ is also a proxy for the pore occupancy and is the thermodynamically appropriate yardstick to determine the loading and composition dependences of intracrystalline diffusivities and diffusion selectivities, S diff. When compared at the same Φ, the component permeabilities, Π i for CO2, CH4, and N2, determinable from CBMC/MD data, are found to be independent of the partners in the various mixtures investigated and have practically the same values as the values for the corresponding unary permeabilities. In all investigated systems, the H2 permeability in a mixture is significantly lower than the corresponding unary value. These reported results have important practical consequences in process development and are also useful for screening of materials for use as membrane devices.

Simultaneous interlayer and intralayer space control in two-dimensional metal-organic frameworks for acetylene/ethylene separation.

Three-dimensional metal-organic frameworks (MOFs) are cutting-edge materials in the adsorptive removal of trace gases due to the availability of abundant pores with specific chemistry. However, the development of ideal adsorbents combining high adsorption capacity with high selectivity and stability remains challenging. Here we demonstrate a strategy to design adsorbents that utilizes the tunability of interlayer and intralayer space of two-dimensional fluorinated MOFs for capturing acetylene from ethylene. Validated by X-ray diffraction and modeling, a systematic variation of linker atom oxidation state enables fine regulation of layer stacking pattern and linker conformation, which affords a strong interlayer trapping of molecules along with cooperative intralayer binding. The resultant robust materials (ZUL-100 and ZUL-200) exhibit benchmark capacity in the pressure range of 0.001-0.05 bar with high selectivity. Their efficiency in acetylene/ethylene separation is confirmed by breakthrough experiments, giving excellent ethylene productivities (121 mmol/g from 1/99 mixture, 99.9999%), even when cycled under moist conditions.

Water/Alcohol Mixture Adsorption in Hydrophobic Materials: Enhanced Water Ingress Caused by Hydrogen Bonding.

Microporous crystalline porous materials such as zeolites, metal-organic frameworks, and zeolitic imidazolate frameworks (ZIFs) have potential use for separating water/alcohol mixtures in fixed bed adsorbers and membrane permeation devices. For recovery of alcohols present in dilute aqueous solutions, the adsorbent materials need to be hydrophobic in order to prevent the ingress of water. The primary objective of this article is to investigate the accuracy of ideal adsorbed solution theory (IAST) for prediction of water/alcohol mixture adsorption in hydrophobic adsorbents. For this purpose, configurational bias Monte Carlo (CBMC) simulations are used to determine the component loadings for adsorption equilibrium of water/methanol and water/ethanol mixtures in all-silica zeolites (CHA, DDR, and FAU) and ZIF-8. Due to the occurrence of strong hydrogen bonding between water and alcohol molecules and attendant clustering, IAST fails to provide quantitative estimates of the component loadings and the adsorption selectivity. For a range of operating conditions, the water loading in the adsorbed phase may exceed that of pure water by one to two orders of magnitude. Furthermore, the occurrence of water-alcohol clusters moderates size entropy effects that prevail under pore saturation conditions. For quantitative modeling of the CBMC, simulated data requires the application of real adsorbed solution theory by incorporation of activity coefficients, suitably parameterized by the Margules model for the excess Gibbs free energy of adsorption.

Using Molecular Simulations for Elucidation of Thermodynamic Nonidealities in Adsorption of CO2-Containing Mixtures in NaX Zeolite.

Cation-exchanged zeolites are of potential use in pressure swing adsorption (PSA) technologies for CO2 capture applications. Published experimental data for CO2/CH4, CO2/N2, and CO2/C3H8 mixture adsorption in NaX zeolite, also commonly referred to by its trade name 13X, have demonstrated that the ideal adsorbed solution theory (IAST) fails to provide adequately accurate estimates of mixture adsorption equilibrium. In particular, the IAST estimates of CO2/CH4 and CO2/N2 selectivities are significantly higher than those realized in experiments. For CO2/C3H8 mixtures, the IAST fails to anticipate the selectivity reversal phenomena observed in experiments. In this article, configurational-bias Monte Carlo (CBMC) simulations are employed to provide confirmation of the observed thermodynamic nonidealities in adsorption of CO2/CH4, CO2/N2, and CO2/C3H8 mixtures in NaX zeolite. The CBMC simulations provide valuable insights into the root cause of the failure of the IAST, whose applicability mandates a homogeneous distribution of adsorbates within the pore landscape. By sampling 105 equilibrated spatial locations of individual guest molecules within the cages of NaX zeolite, the radial distribution functions (RDFs) of each of the pairs of guest molecules are determined. Examination of the RDFs clearly reveals congregation effects, wherein the CO2 guests occupy positions in close proximity to the Na+ cations. The positioning of the partner molecules (CH4, N2, or C3H8) is further removed from the CO2 guest molecules; consequently, the competition in mixture adsorption faced by the partner molecules is less severe than that anticipated by the IAST. The important message to emerge from this article is the need for quantification of thermodynamic nonideality effects in mixture adsorption.

Elucidation of Selectivity Reversals for Binary Mixture Adsorption in Microporous Adsorbents.

The adsorption selectivity, S ads, is a key metric that quantifies the efficacy of any adsorbent in mixture separations. It is common practice to use ideal adsorbed solution theory (IAST) for estimating the value of S ads, using unary isotherm data inputs. In a number of experimental investigations, the phenomena of selectivity reversals and adsorption azeotropy (S ads = 1) have been reported in the published literature; such reversals may result from changes in mixture compositions, pressures, or pore loadings. In many cases, IAST is unable to anticipate such selectivity reversals. In this article, configurational-bias Monte Carlo simulations are used to gain insights into the phenomena of selectivity reversals. Two fundamentally different scenarios of selectivity reversals have been identified. In the first scenario, selectivity reversals are caused by inhomogeneous distribution of adsorbates due to preferential location and siting of a guest species in the pore space. For example, CO2 locates preferentially in the side pockets of mordenite and in window regions of DDR, CHA, and LTA zeolites. CO2 also congregates around the extra-framework cations of NaX zeolite. IAST fails to anticipate such selectivity reversals because its development relies on the assumption that the competition between guest species is uniform within the pore space. In the second scenario, selectivity reversals are caused by entropy effects that manifest near pore saturation conditions; the component that is preferentially adsorbed is the one that has the higher packing efficiency. For a homologous series of compounds, the component with the smaller chain length is favored at high pore occupancies. For adsorption of mixtures of alkane isomers within the intersecting channel network of MFI zeolite, the linear isomer is favored on the basis of entropic considerations.

Commensurate-incommensurate adsorption and diffusion in ordered crystalline microporous materials.

For homologous series of linear chain molecules, there could be either a match, or mismatch, between the characteristic periodicity of the host structure and the characteristic length of the guest molecules. The major objective of this article is to highlight the influence of commensurateness, or incommensurateness, on both the adsorption and diffusion characteristics. Published experimental data, backed by molecular simulation results, are used to highlight the attendant non-monotonicity in adsorption strengths and diffusivities. We demonstrate the possibility of separating mixtures of n-alkanes, n-alcohols, and hydrocarbon isomers by appropriate and judicious choice of the dimensions, topology, and connectivity of the crystalline host material. Of particular practical interest are entropy-based separations that manifest at pore saturation conditions, relying on differences in the saturation capacities of the constituent species; the exploiting of such entropy effects is discussed with the aid of several examples.

Screening metal-organic frameworks for separation of pentane isomers.

This article compares the performances of several metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) for the separation of pentane isomers: n-pentane (nC5), 2-methylbutane (2MB), and 2,2-dimethylpropane (= neo-pentane (neo-P)) in fixed bed adsorbers. The required input data on unary and mixture adsorption equilibria are obtained from Configurational-Bias Monte Carlo (CBMC) simulations for twelve different adsorbents. The best separation performance is realized with Fe2(BDP)3, where BDP2- = 1,4-benzenedipyrazolate, a MOF with triangular shaped 4.9 Å channels that affords the ideal pore topology to differentiate between the three pentane isomers; the linear nC5 aligns commensurately with the pore landscape. Using transient breakthrough simulations in fixed bed adsorbers, the separation performance of Fe2(BDP)3 is found to be significantly superior to that of other materials.

Influence of adsorption thermodynamics on guest diffusivities in nanoporous crystalline materials.

Published experimental data, underpinned by molecular simulations, are used to highlight the strong influence of adsorption thermodynamics on diffusivities of guest molecules inside ordered nanoporous crystalline materials such as zeolites, metal-organic frameworks (MOFs), and zeolitic imidazolate frameworks (ZIFs). For cage-type structures (e.g. LTA, CHA, DDR, and ZIF-8), the variation of the free energy barrier for inter-cage hopping across the narrow windows, -δFi, provides a rationalization of the observed strong influence of pore concentrations, ci, on diffusivities. In open structures with large pore volumes (e.g. FAU, IRMOF-1, CuBTC) and within channels (MFI, BEA, MgMOF-74, MIL-47, MIL-53), the pore concentration (ci) dependence of the self- (Di,self), Maxwell-Stefan (Di), and Fick (Di) diffusivities are often strongly dictated by the inverse thermodynamic correction factor, 1/Γi≡∂ln ci/∂ln pi; the magnitudes of the diffusivities are dictated by the binding energies for adsorption. For many guest-host combinations Di-ci dependence is directly related to the 1/Γivs. ci variation. When molecular clustering occurs, we get 1/Γi > 1, causing unusual Divs. ci dependencies. The match, or mis-match, between the periodicity of the pore landscape and the conformations of adsorbed chain molecules often leads to non-monotonic variation of diffusivities with chain lengths.

Separation of hexane isomers in a metal-organic framework with triangular channels.

Metal-organic frameworks can offer pore geometries that are not available in zeolites or other porous media, facilitating distinct types of shape-based molecular separations. Here, we report Fe2(BDP)3 (BDP(2-) = 1,4-benzenedipyrazolate), a highly stable framework with triangular channels that effect the separation of hexane isomers according to the degree of branching. Consistent with the varying abilities of the isomers to wedge along the triangular corners of the structure, adsorption isotherms and calculated isosteric heats indicate an adsorption selectivity order of n-hexane > 2-methylpentane > 3-methylpentane > 2,3-dimethylbutane ≈ 2,2-dimethylbutane. A breakthrough experiment performed at 160°C with an equimolar mixture of all five molecules confirms that the dibranched isomers elute first from a bed packed with Fe2(BDP)3, followed by the monobranched isomers and finally linear n-hexane. Configurational-bias Monte Carlo simulations confirm the origins of the molecular separation.

In silico screening of metal-organic frameworks in separation applications.

Porous materials such as metal-organic frameworks (MOFs) and zeolitic imidazolate frameworks (ZIFs) offer considerable potential for separating a variety of mixtures such as those relevant for CO(2) capture (CO(2)/H(2), CO(2)/CH(4), CO(2)/N(2)), CH(4)/H(2), alkanes/alkenes, and hydrocarbon isomers. There are basically two different separation technologies that can be employed: (1) a pressure swing adsorption (PSA) unit with a fixed bed of adsorbent particles, and (2) a membrane device, wherein the mixture is allowed to permeate through a micro-porous crystalline layer. In view of the vast number of MOFs, and ZIFs that have been synthesized there is a need for a systematic screening of potential candidates for any given separation task. Also of importance is to investigate how MOFs and ZIFs stack up against the more traditional zeolites such as NaX and NaY with regard to their separation characteristics. This perspective highlights the potency of molecular simulations in determining the choice of the best MOF or ZIF for a given separation task. A variety of metrics that quantify the separation performance, such as adsorption selectivity, working capacity, diffusion selectivity, and membrane permeability, are determined from a combination of Configurational-Bias Monte Carlo (CBMC) and Molecular Dynamics (MD) simulations. The practical utility of the suggested screening methodology is demonstrated by comparison with available experimental data.

Thermosensitive gating effect and selective gas adsorption in a porous coordination nanocage.

A porous coordination nanocage functionalized with 24 triisopropylsilyl groups exhibits a remarkable thermosensitive gate opening phenomenon and demonstrates a molecular sieving effect at a certain temperature range, which can be used for gas separation purposes.

Hydrogen bonding effects in adsorption of water-alcohol mixtures in zeolites and the consequences for the characteristics of the Maxwell-Stefan diffusivities.

This work highlights a variety of peculiar characteristics of adsorption and diffusion of polar molecules such as water, methanol and ethanol in zeolites. These peculiarities are investigated with the aid of configurational-bias Monte Carlo (CBMC) simulations of adsorption isotherms, and molecular dynamics (MD) simulations of diffusivities in FAU, MFI, DDR, and LTA zeolites. Because of strong hydrogen bonding, significant clustering of the guest molecules occurs in all investigated structures. Because of molecular clustering, the inverse thermodynamic factor 1/Gamma(i) identical with (d[ln c(i)])/(d[ln f(i)]) exceeds unity for a range molar concentrations c(i) within the micropores. The degree of clustering is lowered as the temperature is increased. For the concentration ranges for which 1/Gamma(i) > 1, the Fick diffusivity, D(i), for unary diffusion is often lower than both the Maxwell-Stefan, D(i), and the self-diffusivity, D(i,self). For water-alcohol mixtures, the hydrogen bonding between water and alcohol molecules is much more predominant than for water-water, and alcohol-alcohol molecule pairs. Consequently, the adsorption of water-alcohol mixtures shows significant deviations from the predictions of the ideal adsorbed solution theory (IAST). The water-alcohol bonding also leaves its imprint on the mixture diffusion characteristics. The Maxwell-Stefan diffusivity, D(i), of either component in water-alcohol mixtures is lower than the corresponding values of the pure components; this behavior is distinctly different from that for mixtures of nonpolar guest molecules. The binary exchange coefficient D(12) for water-alcohol mixtures is also significantly lower than either self-exchange coefficients D(11) and D(22) of the constituent species. This implies that correlation effects are significantly stronger in water-alcohol mixtures than for the constituent species. Correlation effects are found to be significant for water-alcohol mixture diffusion in DDR and LTA zeolites, even though such effects are negligible for the pure constituents. The major conclusion to emerge from this investigation is that, unlike mixtures of nonpolar molecules, it is not possible to estimate water-alcohol mixture adsorption and diffusion characteristics on the basis of pure component data.

Highlighting a variety of unusual characteristics of adsorption and diffusion in microporous materials induced by clustering of guest molecules.

In this work, we highlight several unusual characteristics of adsorption and diffusion of a variety of guest molecules, such as linear and branched alkanes with a number of C atoms in the 1-6 range, CO(2), and Ar in microporous structures such as zeolites (FAU, NaY) and metal organic frameworks (IRMOF-1, CuBTC, MIL-47, MIL-53 (Cr)-lp, PCN-6') that have channel or cavity sizes larger than about 0.75 nm. Clustering of guest molecules is found to manifest at temperatures below the critical temperature, T(c), of the guest species. The degree of clustering is increased as the temperature, T, is reduced increasingly below T(c). For linear alkanes, T(c) increases with chain length and, consequently, at a given T the degree of clustering increases with increasing chain length. For C4, C5, and C6 alkane isomers, the linear isomer shows a higher degree of clustering than the corresponding branched isomers. Mixture adsorption characteristics are significantly influenced by clustering; specifically, the separation selectivity is found to increased significantly with lowering T. We also discuss the interesting possibility of separating alkane isomer mixtures by exploiting the differences in the degrees of clustering, induced by differences in T(c) of constituent species. An important characteristic of clustering is that the inverse thermodynamic factor 1/Gamma(i) identical with (d ln c(i))/(d ln f(i)) exceeds unity for a range of molar concentrations c(i) within the micropores. For the concentration ranges for which 1/Gamma(i) >1, the Fick diffusivity, D(i), for unary diffusion is often lower than both the Maxwell-Stefan, D(i), and the self-diffusivity, D(i,self). Correlation effects in diffusion are significantly lowered as a consequence of clustering; this reduction in correlation effects is found to have a significant influence on the mixture diffusion characteristics. The diffusion selectivity is significantly affected with increased clustering.

Investigating cluster formation in adsorption of CO2, CH4, and Ar in zeolites and metal organic frameworks at subcritical temperatures.

The critical temperatures, T(c), of CO(2), CH(4), and Ar are 304 K, 191 K, and 151 K, respectively. This paper highlights some unusual characteristics of adsorption and diffusion of these molecules in microporous structures such as zeolites and metal organic frameworks at temperatures T < T(c). Published experimental adsorption data for T < T(c) show that the isotherms invariably display stepped characteristics. The inverse thermodynamic factor 1/Gamma(i) identical with d ln c(i)/d ln f(i) exceeds unity for a range of fugacities f(i) and molar concentrations c(i) within the pore corresponding to the steep portion of the isotherm. With the aid of Monte Carlo simulations of isotherms for different temperatures T < T(c) in a variety of zeolites (AFI, MTW, FAU, NaY, MFI, and MOR), metal-organic frameworks (IRMOF-1, CuBTC, MIL-47 (V), and MIL-53 (Cr)), and covalent-organic frameworks (COF-102, and COF-108), we investigate the conditions required for 1/Gamma(i) > 1. For each of the three species investigated, data on pore concentrations c(i) at any given temperature below T(c) fall within the binodal region for the bulk fluid phase. We present evidence to suggest that, in the concentration ranges for which 1/Gamma(i) > 1, clustering of molecules occurs. The extent of clustering is enhanced as T falls increasingly below T(c). Furthermore, molecular dynamics simulations of diffusion demonstrate that the concentration dependence of the diffusivities is markedly influenced in the regions where 1/Gamma(i) > 1. In regions where molecular clustering occurs, the Fick diffusivity shows, in some cases, a decreasing trend with concentration.

Assessing guest diffusivities in porous hosts from transient concentration profiles.

Using the short-chain-length alkanes from ethane to n-butane as guest molecules, transient concentration profiles during uptake or release (via interference microscopy) and tracer exchange (via IR microimaging) in Zn(tbip), a particularly stable representative of a novel family of nanoporous materials (the metal organic frameworks), were recorded. Analyzing the spatiotemporal dependence of the profiles provides immediate access to the transport diffusivities and self-diffusivities, yielding a data basis of unprecedented reliability for mass transfer in nanoporous materials. As a particular feature of the system, self- and transport diffusivities may be combined to estimate the rate of mutual passages of the guest molecules in the chains of pore segments, thus quantifying departure from a genuine single-file system.