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The vapor phase adsorption of butanol from ABE fermentation at the head space of the fermenter is an interesting route for the efficient recovery of biobutanol. The presence of gases such as carbon dioxide that are produced during the fermentation process causes a stripping of valuable compounds from the aqueous into the vapor phase. This work studies the effect of the presence of carbon dioxide on the adsorption of butanol at a molecular level. With this aim in mind Monte Carlo simulations were employed to study the adsorption of mixtures containing carbon dioxide, butanol and ethanol. Molecular models for butanol and ethanol that reproduce experimental properties of the molecules such as polarity, vapor–liquid coexistence or liquid density have been developed. Pure component isotherms and heats of adsorption have been computed and compared to experimental data to check the accuracy of the interacting parameters. Adsorption of butanol/ethanol mixtures has been studied in absence and presence of CO2 on two representative materials, a pure silica LTA zeolite and a hydrophobic metal–organic framework ZIF-8. To get a better understanding of the molecular mechanism that governs the adsorption of the targeted mixture in the selected materials, the distribution of the molecules inside the structures was analyzed. The combination of these features allows obtaining a deeper understanding of the process and to identify the role of carbon dioxide in the butanol purification process. [ABSTRACT FROM AUTHOR]

A new sulfone functionalized vanadium metal–organic framework (MOF), denoted as SO2-COMOC-2, has been synthesized solvothermally. Its structural and gas sorption properties towards CO2 and CH4 have been evaluated and compared to those of the pristine COMOC-2 material. The SO2-COMOC-2 shows a remarkable increase in CO2 capacity at ambient pressure (2.13 mmol g−1 at 273 K vs. 1.23 mmol g−1 for the pristine COMOC-2). Additionally, the high pressure CO2 sorption isotherm shows a distinctive two-step sorption behavior with a final capacity of 12.45 mmol g−1 for SO2-COMOC-2 at 303 K, while for CH4 a typical Type I isotherm was obtained with a capacity of 4.13 mmol g−1. In situ synchrotron X-ray powder diffraction measurements have been carried out to characterize the structural flexibility of the materials, showing both the presence of large pore and narrow pore form. Furthermore, synchrotron XANES and a variety of spectroscopic techniques have been utilized to verify the presence of hydroxyl groups and the existence of the mixed vanadium oxidation states in the titled MOF structure. [ABSTRACT FROM AUTHOR]

Various metal–organic framework (MOFs) adsorbents show peculiar adsorption behaviour as they can adopt different crystal phases, each phase with its own adsorption characteristics. Besides external stimuli such as temperature or light, different species of guest adsorbate can trigger a transition (breathing) of the host structure at a different pressure. Such phase transitions also occur during dynamic separations on a packed bed of adsorbent, where the concentrations of the adsorbates vary throughout axial column distance and time. This work presents a general strategy to model the adsorption behavior of such phase changing adsorbents during column separations and focuses on remarkable model predictions for pure components and binary mixtures in diluted and non-diluted conditions. During binary breakthrough experiments, the behaviour of flexible adsorbents is quite complex. A succession of complete or even partial phase transformations (resulting in phase coexistence) can occur during the adsorption process. A variety of unusual breakthrough profiles is observed for diluted binary mixtures. Simulations reveal at least five types of breakthrough profiles to emerge. The occurrence of these cases can be rationalized by the hodograph technique, combined with the phase diagram of the adsorbent. The remarkable experimental breakthrough profiles observed for ortho-xylene/ethylbenzene (diluted) and CO2/CH4 (non-diluted) separation on the flexible MIL-53 framework can be rationalized by application of the proposed model strategy. [ABSTRACT FROM AUTHOR]

The electrochemical deposition of Metal–Organic Frameworks (MOFs) is an interesting technique to synthesise adherent, microporous layers on top of conductive substrates. The technique can be subdivided in two approaches: anodic and cathodic deposition. While the mechanism of the cathodic approach has already been well investigated, at least for MOF-5, up to now not much is known about the anodic approach. In this paper, a four-step mechanism is proposed to better understand the anodic deposition, and the same MOF used for the investigation, HKUST-1, is also deposited cathodically to compare the two approaches. This study focuses on how nucleation starts and proceeds, on the influence of the potential applied, the stresses in the growing layers, and the origin of defects like delamination and MOF detachment. The study is followed by critical considerations on the methods and on the technique, together with suggestions and guidelines to synthesise new MOF layers. [ABSTRACT FROM AUTHOR]

The primary goal of this work is to study the adsorption of a wide range of hydrocarbon adsorbates in the Al-fumarate metal–organic framework in order to identify and explore trends in adsorption behaviour that can be related to the sorbate's molecular properties and as well as the properties of this MOF. The pulse chromatographic technique was used to study the adsorption properties of C5–C8 linear, branched, cyclic and aromatic hydrocarbons in vapour phase at low coverage and at high temperatures (150–250 °C). Chromatograms of alkanes having the same number of carbon atoms (C5–C8) clearly show that the linear alkane is retained the longest over its branched and cyclic isomers. Moreover, xylene isomers are also clearly separated by Al-fumarate, with retention times increasing in the order: ortho-xylene ＜ meta-xylene ＜ para-xylene. Differences in adsorption enthalpy of more than 10 kJ mol−1 between linear alkanes and their di/tri-branched or cyclo-alkane isomers were observed, clearly showing that steric effects imposed by the pore structure of the adsorbent cause the difference in adsorption between linear alkanes and their isomers. In conclusion, Al-fumarate behaves as a shape selective material with respect to structural isomers of linear alkanes, with properties resembling those of medium pore size zeolites. [ABSTRACT FROM AUTHOR]

While much attention of the MOF community has been devoted to adsorption and purification of gases, there is now also a vast body of data on the capability of MOFs to separate and purify liquid mixtures. Initial studies focused on separation of petrochemicals in apolar backgrounds, but the attention has moved now to the separation of complex, e.g. chiral compounds, and to the isolation of biobased compounds from aqueous media. We here give an overview of most of the existing literature, with an accent on separation mechanisms and structure-selectivity relationships. [ABSTRACT FROM AUTHOR]

Low-coverage adsorption properties of the metal–organic framework amino-MIL-53 (Al) were determined using the pulse chromatographic technique. By using n-alkanes, iso-alkanes, 1-alkenes, cyclohexane and benzene as probe molecules, the nature of the adsorptive interactions in amino-MIL-53 (Al) was studied. Henry adsorption constants and adsorption enthalpies of iso-alkanes are significantly lower than those of the linear alkanes, demonstrating the shape selective properties of amino-MIL-53. The presence of amino-groups in the pores of the material increases the electrostatic contributions with molecules containing double bonds. A simple model relates adsorption enthalpies to the number of hydrogen atoms and double bonds in the molecule. The effective pore size of the material was estimated based on the relationship between adsorption enthalpy and entropy. [ABSTRACT FROM AUTHOR]

A new sulfone functionalized vanadium metal-organic framework (MOF), denoted as SO2-COMOC-2, has been synthesized solvothermally. Its structural and gas sorption properties towards CO2 and CH4 have been evaluated and compared to those of the pristine COMOC-2 material. The SO2-COMOC-2 shows a remarkable increase in CO2 capacity at ambient pressure (2.13 mmol g(-1) at 273 K vs. 1.23 mmol g(-1) for the pristine COMOC-2). Additionally, the high pressure CO2 sorption isotherm shows a distinctive two-step sorption behavior with a final capacity of 12.45 mmol g(-1) for SO2-COMOC-2 at 303 K, while for CH4 a typical Type I isotherm was obtained with a capacity of 4.13 mmol g(-1). In situ synchrotron X-ray powder diffraction measurements have been carried out to characterize the structural flexibility of the materials, showing both the presence of large pore and narrow pore form. Furthermore, synchrotron XANES and a variety of spectroscopic techniques have been utilized to verify the presence of hydroxyl groups and the existence of the mixed vanadium oxidation states in the titled MOF structure.

Various metal-organic framework (MOFs) adsorbents show peculiar adsorption behaviour as they can adopt different crystal phases, each phase with its own adsorption characteristics. Besides external stimuli such as temperature or light, different species of guest adsorbate can trigger a transition (breathing) of the host structure at a different pressure. Such phase transitions also occur during dynamic separations on a packed bed of adsorbent, where the concentrations of the adsorbates vary throughout axial column distance and time. This work presents a general strategy to model the adsorption behavior of such phase changing adsorbents during column separations and focuses on remarkable model predictions for pure components and binary mixtures in diluted and non-diluted conditions. During binary breakthrough experiments, the behaviour of flexible adsorbents is quite complex. A succession of complete or even partial phase transformations (resulting in phase coexistence) can occur during the adsorption process. A variety of unusual breakthrough profiles is observed for diluted binary mixtures. Simulations reveal at least five types of breakthrough profiles to emerge. The occurrence of these cases can be rationalized by the hodograph technique, combined with the phase diagram of the adsorbent. The remarkable experimental breakthrough profiles observed for ortho-xylene/ethylbenzene (diluted) and CO2/CH4 (non-diluted) separation on the flexible MIL-53 framework can be rationalized by application of the proposed model strategy.

Two perfluorinated metal hydroxo terephthalates [M(III)(OH)(BDC-F)]·n(guests) (M(III) = V, MIL-47-F-AS or 1-AS; Al, Al-MIL-53-F-AS or 2-AS) (BDC-F = 2-fluoro-1,4-benzenedicarboxylate; AS = as-synthesized) have been synthesized by a hydrothermal method using microwave irradiation (1-AS) or conventional electric heating (2-AS), respectively. The unreacted or occluded H(2)BDC-F molecules can be removed under vacuum by direct thermal activation or exchange of guest molecules followed by thermal treatment leading to the empty-pore forms of the title compounds [V(IV)(O)(BDC-F)] (MIL-47-F, 1) and [Al(III)(OH)(BDC-F)] (Al-MIL-53-F, 2). Thermogravimetric analysis (TGA) and temperature-dependent XRPD (TDXRPD) experiments indicate that the compounds are stable up to 385 and 480 °C, respectively. Both of the thermally activated compounds exhibit significant microporosity, as verified by N(2), CO(2), n-hexane, o- and p-xylene sorption analyses. The structural changes of 2 upon adsorption of CO(2), n-hexane, o- and p-xylene were highly influenced due to functionalization by -F groups, as compared to parent Al-MIL-53. The -F groups also introduce a certain degree of hydrophobicity into the frameworks, as demonstrated by the H(2)O sorption analyses.

An amino functionalized vanadium-containing Metal Organic Framework, NH(2)-MIL-47, has been synthesized by a hydrothermal reaction in an autoclave. Alternatively, a synthesis route via microwave enhanced irradiation has been optimized to accelerate the synthesis. The NH(2)-MIL-47 exhibits the same topology as MIL-47, in which the V center is octahedrally coordinated. After an exchange procedure in DMF the V(+III) center is oxidized to V(+IV), which is confirmed by EPR and XPS measurements. The CO(2) and CH(4) adsorption properties have been evaluated and compared to MIL-47, showing that both MOFs have an almost similar adsorption capacity and affinity for CO(2). DFT-based molecular modeling calculations were performed to obtain more insight into the adsorption positions for CO(2) in NH(2)-MIL-47. Furthermore our calculated adsorption enthalpies agree well with the experimental values.

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.

Molecular dynamics (MD) simulations have been performed to investigate the rotational diffusive motion for 2-methyl butane (2-MeC4) and n-pentane (n-C5) in the cages of MCM-22 zeolite from 200-340 K. The rotation intermediate scattering function I(R) (Q,t) for 2-MeC4 and n-C5 confined in the supercages of MCM-22 was calculated. The dynamic scattering functions S(inc)(Q,omega) obtained via Fourier transformation of this intermediate scattering function are in good agreement with those of quasi-elastic neutron scattering experiments. The rotational intermediate scattering functions of 2-MeC4 decay more rapidly than those of n-C5 before 1.0 ps. In the longer time region, the rotational intermediate scattering functions of both molecules intersect. It is shown that n-C5 molecules move more easily from supercage to supercage compared to 2-MeC4, rotating for a longer time in the confinement of the MCM-22 supercage.

The capacity and selectivity of the metal-organic framework MIL-47 for liquid phase adsorption are shown to heavily depend on the pretreatment of the material, as illustrated in detail by the particular case of selective xylene adsorption. By totally removing the uncoordinated terephthalic acid from the pores and simultaneously avoiding oxidation to nonporous V(2)O(5), pore volume and uptake of xylenes can be maximized. The presence of uncoordinated terephthalic acid in the pores improves the selectivity between p- and m-xylene. Calcination bed thickness and oven geometry influence the optimal calcination procedure. The physicochemical modifications of MIL-47 during its activation are investigated in detail with XRD, SEM, nitrogen physisorption, TGA and diffuse reflectance UV-Vis spectroscopy. Using optimally pretreated MIL-47 as adsorbent for xylene, ethyltoluene, dichlorobenzene, toluidine or cresol isomers, the para-isomer is in each case preferred over the meta-isomer in pulse chromatographic and batch experiments. The role of stacking in the selective adsorption of these isomers is discussed. In the case of the dichlorobenzenes, the meta- and para-isomers can be separated in a breakthrough experiment with a selectivity of 5.0.

In the adsorption of linear C1-C8 alkanes, alkenes and alcohols on zeolite chabazite, molecules smaller than 6.7 A are adsorbed in significant amounts, whereas longer chains are almost fully excluded from the micropores.

n-Alkane hydroisomerisation and hydrocracking experiments reveal that ZSM-5 materials synthesized by self-assembly of nanoslabs show different molecular shape selectivity than ZSM-5 synthesized by hydrothermal methods.