scholarly journals Statistical mechanics of binary mixture adsorption in metal–organic frameworks in the osmotic ensemble

2018 ◽  
Vol 376 (2115) ◽  
pp. 20170151 ◽  
Author(s):  
Lawrence J. Dunne ◽  
George Manos
Keyword(s):  
Binary Mixture ◽  
Adsorption Isotherms ◽  
Good Description ◽  
Metal Organic Frameworks ◽  
Co Adsorption ◽  
Experimental Parameter ◽  
Separation Processes ◽  
Mixture Adsorption ◽  
Wide Range ◽  
Metal Organic

Although crucial for designing separation processes little is known experimentally about multi-component adsorption isotherms in comparison with pure single components. Very few binary mixture adsorption isotherms are to be found in the literature and information about isotherms over a wide range of gas-phase composition and mechanical pressures and temperature is lacking. Here, we present a quasi-one-dimensional statistical mechanical model of binary mixture adsorption in metal–organic frameworks (MOFs) treated exactly by a transfer matrix method in the osmotic ensemble. The experimental parameter space may be very complex and investigations into multi-component mixture adsorption may be guided by theoretical insights. The approach successfully models breathing structural transitions induced by adsorption giving a good account of the shape of adsorption isotherms of CO 2 and CH 4 adsorption in MIL-53(Al). Binary mixture isotherms and co-adsorption-phase diagrams are also calculated and found to give a good description of the experimental trends in these properties and because of the wide model parameter range which reproduces this behaviour suggests that this is generic to MOFs. Finally, a study is made of the influence of mechanical pressure on the shape of CO 2 and CH 4 adsorption isotherms in MIL-53(Al). Quite modest mechanical pressures can induce significant changes to isotherm shapes in MOFs with implications for binary mixture separation processes. This article is part of the theme issue ‘Modern theoretical chemistry’.

scholarly journals The effect of atomic point charges on adsorption isotherms of CO2 and water in metal organic frameworks

Adsorption ◽  
2019 ◽  
Vol 26 (5) ◽  
pp. 663-685 ◽  
Author(s):  
Kristina Sladekova ◽  
Christopher Campbell ◽  
Calum Grant ◽  
Ashleigh J. Fletcher ◽  
José R. B. Gomes ◽  
...  
Keyword(s):  
Adsorption Isotherms ◽  
Point Charge ◽  
Carbon Capture ◽  
Gas Adsorption ◽  
Periodic Structures ◽  
Metal Organic Frameworks ◽  
Large Variability ◽  
Wide Range ◽  
Open Metal Sites ◽  
Metal Organic

AbstractThe interactions between metal–organic frameworks (MOFs) and adsorbates have been increasingly predicted and studied by computer simulations, particularly by Grand-Canonical Monte Carlo (GCMC), as this method enables comparing the results with experimental data and also provides a degree of molecular level detail that is difficult to obtain in experiments. The assignment of atomic point charges to each atom of the framework is essential for modelling Coulombic interactions between the MOF and the adsorbate. Such interactions are important in adsorption of polar gases like water or carbon dioxide, both of which are central in carbon capture processes. The aim of this work is to systematically investigate the effect of varying atomic point charges on adsorption isotherm predictions, identify the underlying trends, and based on this knowledge to improve existing models in order to increase the accuracy of gas adsorption prediction in MOFs. Adsorption isotherms for CO2 and water in several MOFs were generated with GCMC, using the same computational parameters for each material except framework point charge sets that were obtained through a wide range of computational approaches. We carried out this work for 6 widely studied MOFs; IRMOF-1, MIL-47, UiO-66, CuBTC, Co-MOF-74 and SIFSIX-2-Cu-I. We included both MOFs with and without open metal sites (OMS), specifically to investigate whether this property affects the predicted adsorption behaviour. Our results show that point charges obtained from quantum mechanical calculations on fully periodic structures are generally more consistent and reliable than those obtained from either cluster-based QM calculations or semi-empirical approaches. Furthermore, adsorption in MOFs that contain OMS is much more sensitive to the point charge values, with particularly large variability being observed for water adsorption in such MOFs. This suggests that particular care must be taken when simulating adsorption of polar molecules in MOFs with open metal sites to ensure that accurate results are obtained.

scholarly journals Prediction of Breathing and Gate-Opening Transitions Upon Binary Mixture Adsorption in Metal−Organic Frameworks

2009 ◽  
Vol 131 (32) ◽  
pp. 11329-11331 ◽  
Author(s):  
François-Xavier Coudert ◽  
Caroline Mellot-Draznieks ◽  
Alain H. Fuchs ◽  
Anne Boutin
Keyword(s):  
Binary Mixture ◽  
Metal Organic Frameworks ◽  
Gate Opening ◽  
Mixture Adsorption ◽  
Metal Organic

scholarly journals In situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)-based Metal-Organic Frameworks with UiO-66 and MIL-140 architectures

2020 ◽  
Author(s):  
Stephen Shearan ◽  
Jannick Jacobsen ◽  
Ferdinando Costantino ◽  
Roberto D’Amato ◽  
Dmitri Novikov ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Metal Organic Frameworks ◽  
Building Blocks ◽  
Nucleation And Growth ◽  
X Ray Diffraction ◽  
X Ray ◽  
Rate Determining Step ◽  
Wide Range ◽  
Metal Organic

We report on the results of a thorough <i>in situ</i> synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds <i>in situ</i> in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO<sub>3</sub>) and amount of the coordination modulator acetic acid (AcOH). When only HNO<sub>3</sub> is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO<sub>3</sub>, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO<sub>3</sub> slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO<sub>3</sub> favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO<sub>3</sub>. Based on these <i>in situ</i> results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

scholarly journals MOF thin films with bi-aromatic linkers grown by molecular layer deposition

2020 ◽  
Vol 8 (5) ◽  
pp. 2539-2548 ◽  
Author(s):  
Kristian Blindheim Lausund ◽  
Malin Solheim Olsen ◽  
Per-Anders Hansen ◽  
Håkon Valen ◽  
Ola Nilsen
Keyword(s):  
Thin Films ◽  
Molecular Layer ◽  
Metal Organic Frameworks ◽  
Molecular Layer Deposition ◽  
Layer Deposition ◽  
Wide Range ◽  
Metal Organic ◽  
Sensor Materials

Thin films of metal–organic frameworks (MOFs) are promising for a wide range of applications including membranes for separations and sensor materials in microelectronics.

A family of doped lanthanide metal–organic frameworks for wide-range temperature sensing and tunable white light emission

2017 ◽  
Vol 5 (8) ◽  
pp. 1981-1989 ◽  
Author(s):  
Yan Yang ◽  
Lian Chen ◽  
Feilong Jiang ◽  
Muxin Yu ◽  
Xiuyan Wan ◽  
...  
Keyword(s):  
White Light ◽  
High Stability ◽  
Light Emission ◽  
Metal Organic Frameworks ◽  
Temperature Sensing ◽  
White Leds ◽  
Wide Range ◽  
Potential Applications ◽  
Metal Organic ◽  
Lanthanide Metal

A series of binary and ternary mixed LnMOFs with high stability showing potential applications in wide-range thermosensors and white LEDs are reported.

Understanding Inflections and Steps in Carbon Dioxide Adsorption Isotherms in Metal-Organic Frameworks

2008 ◽  
Vol 130 (2) ◽  
pp. 406-407 ◽  
Author(s):  
Krista S. Walton ◽  
Andrew R. Millward ◽  
David Dubbeldam ◽  
Houston Frost ◽  
John J. Low ◽  
...  
Keyword(s):  
Carbon Dioxide ◽  
Adsorption Isotherms ◽  
Metal Organic Frameworks ◽  
Carbon Dioxide Adsorption ◽  
Metal Organic

scholarly journals High-Throughput Screening of Metal–organic Frameworks for Macroscale Heteroepitaxial Alignment

2018 ◽  
Author(s):  
Andrew Tarzia ◽  
Masahide Takahashi ◽  
Paolo Falcaro ◽  
Aaron Thornton ◽  
Christian Doonan ◽  
...  
Keyword(s):  
High Throughput ◽  
High Throughput Screening ◽  
Defect Formation ◽  
Metal Organic Frameworks ◽  
Rectangular Lattice ◽  
Copper Hydroxide ◽  
Computational Screening ◽  
Screening Algorithm ◽  
Wide Range ◽  
Metal Organic

The ability to align porous metal–organic frameworks (MOFs) on substrate surfaces on a macroscopic scale is a vital step towards integrating MOFs into functional devices. But macroscale surface alignment of MOF crystals has only been demonstrated in a few cases. To accelerate the materials discovery process, we have developed a high-throughput computational screening algorithm to identify MOFs that are likely to undergo macroscale aligned heterepitaxial growth on a substrate. Screening of thousands of MOF structures by this process can be achieved in a few days on a desktop workstation. The algorithm filters MOFs based on surface chemical compatibility, lattice matching with the substrate, and interfacial bonding. Our method uses a simple new computationally efficient measure of the interfacial energy that considers both bond and defect formation at the interface. Furthermore, we show that this novel descriptor is a better predictor of aligned heteroepitaxial growth than other established interface descriptors, by testing our screening algorithm on a sample set of copper MOFs that have been grown heteroepitaxially on a copper hydroxide surface. Application of the screening process to several MOF databases reveals that the top candidates for aligned growth on copper hydroxide comprise mostly MOFs with rectangular lattice symmetry in the plane of the substrate. This result indicates a substrate-directing effect that could be exploited in targeted synthetic strategies. We also identify that MOFs likely to form aligned heterostructures have broad distributions of in-plane pore sizes and anisotropies. Accordingly, this suggests that aligned MOF thin films with a wide range of properties may be experimentally accessible.

scholarly journals High-Throughput Screening of Metal–organic Frameworks for Macroscale Heteroepitaxial Alignment

2018 ◽  
Author(s):  
Andrew Tarzia ◽  
Masahide Takahashi ◽  
Paolo Falcaro ◽  
Aaron Thornton ◽  
Christian Doonan ◽  
...  
Keyword(s):  
High Throughput ◽  
High Throughput Screening ◽  
Defect Formation ◽  
Metal Organic Frameworks ◽  
Rectangular Lattice ◽  
Copper Hydroxide ◽  
Computational Screening ◽  
Screening Algorithm ◽  
Wide Range ◽  
Metal Organic

The ability to align porous metal–organic frameworks (MOFs) on substrate surfaces on a macroscopic scale is a vital step towards integrating MOFs into functional devices. But macroscale surface alignment of MOF crystals has only been demonstrated in a few cases. To accelerate the materials discovery process, we have developed a high-throughput computational screening algorithm to identify MOFs that are likely to undergo macroscale aligned heterepitaxial growth on a substrate. Screening of thousands of MOF structures by this process can be achieved in a few days on a desktop workstation. The algorithm filters MOFs based on surface chemical compatibility, lattice matching with the substrate, and interfacial bonding. Our method uses a simple new computationally efficient measure of the interfacial energy that considers both bond and defect formation at the interface. Furthermore, we show that this novel descriptor is a better predictor of aligned heteroepitaxial growth than other established interface descriptors, by testing our screening algorithm on a sample set of copper MOFs that have been grown heteroepitaxially on a copper hydroxide surface. Application of the screening process to several MOF databases reveals that the top candidates for aligned growth on copper hydroxide comprise mostly MOFs with rectangular lattice symmetry in the plane of the substrate. This result indicates a substrate-directing effect that could be exploited in targeted synthetic strategies. We also identify that MOFs likely to form aligned heterostructures have broad distributions of in-plane pore sizes and anisotropies. Accordingly, this suggests that aligned MOF thin films with a wide range of properties may be experimentally accessible.

scholarly journals Upgrading the Hydrogen Storage of MOF-5 by Post-Synthetic Exchange with Divalent Metal Ions

2021 ◽  
Vol 11 (24) ◽  
pp. 11687
Author(s):  
Abdul Malik P. Peedikakkal ◽  
Isam H. Aljundi
Keyword(s):  
Metal Ions ◽  
Adsorption Isotherms ◽  
Metal Organic Frameworks ◽  
Hydrogen Uptake ◽  
Metal Exchange ◽  
Mixed Metal ◽  
H2 Adsorption ◽  
Hydrogen Molecules ◽  
Metal Metal ◽  
Metal Organic

In metal-organic frameworks (MOFs), mixed-metal clusters have the opportunity to adsorb hydrogen molecules due to a greater charge density of the metal. Such interactions may subsequently enhance the gravimetric uptake of hydrogen. However, only a few papers have explored the ability of mixed-metal MOFs to increase hydrogen uptake. The present work reveals the preparation of mixed metal metal-organic frameworks M-MOF-5 (where M = Ni2+, Co2+, and Fe2+) (where MOF-5 designates MOFs such as Zn2+ and 1,4-benzenedicarboxylic acid ligand) using the post-synthetic exchange (PSE) technique. Powder X-ray diffraction patterns and scanning electron microscopy images indicate the presence of crystalline phases after metal exchange, and the inductively coupled plasma–mass spectroscopy analysis confirmed the exchange of metals by means of the PSE technique. The nitrogen adsorption isotherms established the production of microporous M-MOF-5. Although the additional metal ions decreased the surface area, the exchanged materials displayed unique features in the gravimetric uptake of hydrogen. The parent MOF-5 and the metal exchanged materials (Ni-MOF-5, Co-MOF-5, and Fe-MOF-5) demonstrated hydrogen capacities of 1.46, 1.53, 1.53, and 0.99 wt.%, respectively. The metal-exchanged Ni-MOF-5 and Co-MOF-5 revealed slightly higher H2 uptake in comparison with MOF-5; however, the Fe-MOF-5 showed a decrease in uptake due to partial discrete complex formation (discrete complexes with one or more metal ions) with less crystalline nature. The Sips model was found to be excellent in describing the H2 adsorption isotherms with a correlation coefficient ≅ 1. The unique hydrogen uptakes of Ni− and Co-MOF-5 shown in this study pave the way for further improvement in hydrogen uptake.

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