The effect of pore shape on hydrocarbon selectivity on UiO-66(Zr), HKUST-1 and MIL-125(Ti) metal organic frameworks: Insights from molecular simulations and chromatography

Ramsahye, Naseem A.; Trens, Philippe; Shepherd, Céline; Gonzalez, Philippe; Trung, Thuy Khuong; Ragon, Florence; Serre, Christian

doi:10.1016/j.micromeso.2013.09.005

Cited by 57 publications

(57 citation statements)

References 52 publications

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“…For example, the passage from one octahedral cage to another shall take place via a tetrahedral cage. 27 In the case of the hydroxylated UiO-66(Zr), the presence of μ-OH groups results in two distinct types of tetrahedral cavity. The hydroxyl groups are located in the slightly larger of the two tetrahedral cavities.…”

Section: Framework Of Uio-66mentioning

confidence: 99%

“…In order to diffuse in UiO‐66, molecules need to move from one type of cage to the other. For example, the passage from one octahedral cage to another shall take place via a tetrahedral cage 27 . In the case of the hydroxylated UiO‐66(Zr), the presence of μ ‐OH groups results in two distinct types of tetrahedral cavity.…”

Section: Model and Calculation Detailsmentioning

confidence: 99%

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A computational study of water in UiO‐66 Zr‐MOFs: Diffusion, hydrogen bonding network, and confinement effect

et al. 2020

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For chemical warfare agent removal, the humidity emerges as an unavoidable challenge that significantly affects the performance of metal-organic frameworks. In this work, via density functional theory calculations, ab initio molecular dynamics and classical molecular dynamics simulations, we investigate the structural and diffusion properties of water in the pristine defect-free UiO-66, one Zr-based metal-organic framework. Through the detailed analyses of the distribution probability of water in two different cages of UiO-66, the binding interaction between water and UiO-66, the hydrogen bonding networks and resulted localized water clusters, we gain a fundamental understanding of structural and dynamics properties as well as the concentration dependence of water in UiO-66. We anticipate those theoretical results could provide insight to the competitive adsorption of water and chemical warfare agents, which eventually shows the utmost importance for the design and development of the next generation porous materials with appropriate water properties in real-life applications.

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Section: Framework Of Uio-66mentioning

confidence: 99%

Section: Model and Calculation Detailsmentioning

confidence: 99%

A computational study of water in UiO‐66 Zr‐MOFs: Diffusion, hydrogen bonding network, and confinement effect

et al. 2020

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“…60-80 kJ/mol for C 6 isomers in UiO-66 and HKUST-1). 16,30 Table 2. "Normalized" molar enthalpy of immersion for the different MOFs evaluated (kJ per mol of adsorbed hydrocarbon) estimated from the immersion calorimetry measurements and considering the total amount adsorbed in the vapor adsorption experiments.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

“…To help the understanding of the adsorption phenomena in MOFs, 15,16 Despite the technological importance of this phenomenon, the number of experimental studies dealing with inverse selectivity is scarce, whereas the adsorption phenomena at the molecular level is difficult to understand.…”

Section: Introductionmentioning

confidence: 99%

Reverse Hierarchy of Alkane Adsorption in Metal–Organic Frameworks (MOFs) Revealed by Immersion Calorimetry

et al. 2019

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Immersion calorimetry into liquids of different dimensions is a powerful tool to learn about the pore size and shape in nanoporous solids. In general, in the absence of specific interactions with the solid surface, the accessibility of the liquid probe molecule to the inner porosity, and the associated enthalpy value decreases with an increase in its kinetic diameter (bulkier molecules have lower accessibility and packing density). Although this is true for majority of solids (e.g. activated carbons and zeolites), this study anticipates that this is not straightforward in the specific case of MOFs. The evaluation of different hydrocarbons and their derivatives reveals the presence of reverse selectivity for C 6 isomers (2,2-dimethylbutane>2-methylpentane>n-hexane) in UiO-66 and HKUST-1, while size exclusion effects take place in ZIF-8. The immersion calorimetric findings have been compared with vapor adsorption isotherms and computational studies. Monte Carlo simulations suggest that the reverse selectivity in UiO-66 are attributed to the strong confinement of the di-branched hydrocarbons in the small tetragonal cages, while the presence of strong interactions with the open metal sites account for the preferential adsorption in HKUST-1. These results open the gate towards the application of immersion calorimetry for the pre-

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“…Chemical and physical tunability of the MOF structures during synthesis is the most important advantage of MOFs over other traditional adsorbent and membrane materials. Numerous MOFs have been synthesized to date and their good potential in gas separation processes has been recognized in several experimental and computational studies …”

Section: Introductionmentioning

confidence: 99%

Effects of molecular simulation parameters on predicting gas separation performance of ZIFs

Ozcan

Keskin

2014

J. Chem. Technol. Biotechnol.

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BACKGROUND: A significant number of molecular simulation studies exist in the literature for assessing single-component gas adsorption capacities of ZIFs and all these simulations were performed using different force field parameters. In this study, molecular simulations were carried out to predict both adsorption-based and membrane-based separation performances of ZIF-68 and ZIF-69 for CH 4 /H 2 , CH 4 /N 2 , CO 2 /CH 4 , CO 2 /H 2 and CO 2 /N 2 mixtures using three different force fields. RESULTS:Results showed that adsorption selectivity of ZIFs may vary significantly depending on the force field parameters whereas membrane selectivity is much less sensitive to the force field. In addition to adsorption and membrane selectivities, various separation properties of ZIFs were estimated such as working capacity, sorbent selection parameter, regenerability, permeability and compared with the properties of other well-known nanoporous adsorbents and membranes. CONCLUSION: Comparison of separation performance of ZIF-68 and ZIF-69 with traditional zeolites showed that ZIFs can be promising adsorbent materials for CH 4 /H 2 , CH 4 /N 2 , CO 2 /CH 4 , CO 2 /H 2 separations and promising membrane materials for CH 4 /H 2 and CO 2 /H 2 separations. It is better to use ZIFs as adsorbents rather than membranes since they offer higher adsorption selectivity than permeation selectivity for the gas mixtures we studied. A Ozcan, S Keskin based on two generic FFs, UFF and DREIDING; 21 Sirjoosingh et al. 22 simulated CO 2 and CO adsorption in ZIF-68 and ZIF-69 using UFF; Hou and Li 23 studied CO 2 adsorption in ZIF-68 and ZIF-69 using UFF; Prakash et al. 24 also simulated H 2 , N 2 , CH 4 adsorption in ZIF-95 and ZIF-100 using self-calculated Morse potential parameters; Li et al. 25 evaluated N 2 , CH 4 , CO 2 selectivity of ZIF-78 and ZIF-79 using UFF, DREIDING and refined UFF parameters. 19 The number of studies on gas diffusion simulations of ZIFs is very limited compared with gas adsorption simulations. Using UFF, Rankin et al. 26 reported diffusion of H 2 , CH 4 and CO 2 in ZIF-68 and ZIF-70; Sirjoosingh and co-workers 22 examined diffusion of CO 2 and CO in ZIF-68 and ZIF-69; Liu et al. 17 studied CO 2 diffusion in ZIF-68 and ZIF-69; Babarao et al. 20 examined diffusion of CO 2 in ZIF-68. Atci and Keskin 27 reported the first data for mixture diffusion in ZIFs by computing self-diffusivities of CH 4 /H 2 , CO 2 /CH 4 , CO 2 /H 2 mixtures in 15 different ZIFs using UFF and DREIDING.As can be seen from this brief literature review, different FFs, both generic (UFF and DREIDING) and new ones (Liu FF) have been used to estimate the adsorption isotherms and/or diffusion coefficients of gases in ZIFs. In most cases, accuracy of the FF is validated by comparing the experimentally measured single-component gas adsorption isotherms with the simulated ones. However, there is no study of the effect of FFs on computing mixture adsorption isotherms and mixture diffusivities in ZIFs. More importantly, it is currently not known how the choi...

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The effect of pore shape on hydrocarbon selectivity on UiO-66(Zr), HKUST-1 and MIL-125(Ti) metal organic frameworks: Insights from molecular simulations and chromatography

Cited by 57 publications

References 52 publications

A computational study of water in UiO‐66 Zr‐MOFs: Diffusion, hydrogen bonding network, and confinement effect

A computational study of water in UiO‐66 Zr‐MOFs: Diffusion, hydrogen bonding network, and confinement effect

Reverse Hierarchy of Alkane Adsorption in Metal–Organic Frameworks (MOFs) Revealed by Immersion Calorimetry

Effects of molecular simulation parameters on predicting gas separation performance of ZIFs

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