Theoretical Investigations of CO<sub>2</sub> and CH<sub>4</sub> Sorption in an Interpenetrated Diamondoid Metal–Organic Material

Pham, Tony; Forrest, Katherine A.; Tudor, Brant; Elsaidi, Sameh K.; Mohamed, Mona H.; McLaughlin, K. L.; Cioce, Christian R.; Zaworotko, Michael J.; Space, Brian

doi:10.1021/la500967w

Cited by 36 publications

(30 citation statements)

References 60 publications

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“…The development of the force field for In-soc-MOF was performed according to the procedure described in previous work. 12,24,25,[29][30][31][32][33][34][35][36][37][38][39][40][41] Nevertheless, a brief outline is given here. For all C, H, and N atoms on the organic linker in In-soc-MOF, the Lennard-Jones 12-6 parameters, representing van der Waals interactions between the sorbate molecules and the MOF atoms, were acquired from the Optimized Potentials for Liquid Simulations -All Atom (OPLS-AA) force field.…”

Section: A Mof Parametersmentioning

confidence: 99%

Understanding Hydrogen Sorption in In-soc-MOF: A Charged Metal-Organic Framework with Open-Metal Sites, Narrow Channels, and Counterions

Pham

Forrest

Hogan

et al. 2015

Crystal Growth & Design

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Grand canonical Monte Carlo (GCMC) simulations of hydrogen sorption were performed in In-soc-MOF, a charged metal-organic framework (MOF) that contains In3O trimers coordinated to 5,5 -azobis-1,3-benzenedicarboxylate linkers. The MOF contains nitrate counterions that are located in carcerand-like capsules of the framework. This MOF was shown to have a high hydrogen uptake at 77 K and 1.0 atm. The simulations were performed with a potential that includes explicit many-body polarization interactions, which were important for modeling gas sorption in a charged/polar MOF such as In-soc-MOF. The simulated hydrogen sorption isotherms were in good agreement with experiment in this challenging platform for modeling. The simulations predict a high initial isosteric heat of adsorption, Qst, value of about 8.5 kJ mol −1 , which is in contrast to the experimental value of 6.5 kJ mol −1 for all loadings. The difference in the Qst behavior between experiment and simulation is attributed to the fact that, in experimental measurements, the sorbate molecules cannot access the isolated cages containing the nitrate ions, the most energetically favorable site in the MOF, at low pressures due to an observed diffusional barrier. In contrast, the simulations were able to capture the sorption of hydrogen onto the nitrate ions at low loading due to the equilibrium nature of GCMC simulations. The experimental Qst values were reproduced in simulation by blocking access to all of the nitrate ions in the MOF. Furthermore, at 77 K, the sorbed hydrogen molecules were reminiscent of a dense fluid in In-soc-MOF starting at approximately 5.0 atm, and this was verified by monitoring the isothermal compressibility, βT , values. The favorable sites for hydrogen sorption were identified from the polarization distribution as the nitrate ions, the In3O trimers, and the azobenzene nitrogen atoms. Lastly, the two-dimensional quantum rotational levels for a hydrogen molecule sorbed about the aforementioned sites were calculated and the transitions were in good agreement to those that were observed in the experimental inelastic neutron scattering (INS) spectra.

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Section: A Mof Parametersmentioning

confidence: 99%

Understanding Hydrogen Sorption in In-soc-MOF: A Charged Metal-Organic Framework with Open-Metal Sites, Narrow Channels, and Counterions

Pham

Forrest

Hogan

et al. 2015

Crystal Growth & Design

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“…It is to note that further lowering of temperature to 273.15 K improved the ΔG values. The free energy values at 273.15 K are not largely different due to its large quadruple moment that also prevails at 298 K (Tc = 304.4 K) . The calculated desorption energies for each complex are mentioned in Table .…”

Section: Resultsmentioning

confidence: 93%

“…Therefore, lowering the temperature or increasing the pressure are recommended to facilitate the H 2 adsorption process (Table ). H 2 is a supercritical gas at 298 K (Tc =33.2 K), and it interacts very weakly with its environment under such ambient conditions . Therefore, the free energy calculations performed at 273.15 K leads to the more negative ΔG values for H 2 adsorption process (Table ).…”

Section: Resultsmentioning

confidence: 99%

“…H 2 is a supercritical gas at 298 K (Tc =33.2 K), and it interacts very weakly with its environment under such ambient conditions. [12] Therefore, the free energy calculations performed at 273.15 K leads to the more negative ΔG values for H 2 adsorption process (Table 4). Desorption is the reverse of the adsorption process for release of the gas molecules from the stored materials.…”

Section: Atoms In Molecules (Aim) Analysismentioning

confidence: 92%

“…The free energy values at 273.15 K are not largely different due to its large quadruple moment that also prevails at 298 K (Tc = 304.4 K). [12] The calculated desorption energies for each complex are mentioned in Table 7. The single point energy calculations performed for the adsorption of CO 2 with these cyclopropane systems using cc-pVDZ basis set are in good agreement with M06-2X/6-31G(d) results (Table S2).…”

Section: Carbon Dioxide Adsorption Studymentioning

confidence: 99%

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Probing the bent bonds in cyclopropane systems for gas storage and separation process: A computational study

Wakchaure

Ganguly

2020

J Comput Chem

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The hydrogen, carbon dioxide, and carbon monoxide gas adsorption and storage capacity of lithium‐decorated cyclopropane ring systems were examined with quantum chemical calculations at density functional theory, DFT M06‐2X functional using 6‐31G(d) and cc‐pVDZ basis sets. To examine the reliability of M06‐2X DFT functional, a few representative systems are also examined with complete basis set CBS‐QB3 method and CCSD‐aug‐cc‐pVTZ level of theory. The cyclopropane systems can bind to one Li+ ion; however, the corresponding the methylated systems can bind with two Li+ ions. The cyclopropane systems can adsorb six hydrogen molecules with an average binding energy of 3.8 kcal/mol. The binding free energy (ΔG) values suggest that the hydrogen adsorption process is feasible at 273.15 K. The calculation of desorption energies indicates the recyclable property of gas adsorbed complexes. The same number of CO2 and CO gas molecules can also be adsorbed with an average binding energy of −14.4 kcal/mol and −10.7 kcal/mol, respectively. The carbon dioxide showed ~3–4 kcal/mol better binding energy as compared to carbon monoxide and hence such designed systems can function as a potential candidate for the separation of these flue gas molecules. The nature of interactions in complexes was examined with atoms in molecules analysis revealed the electrostatic nature for the interaction of Li+ ion with cyclopropane rings. The chemical hardness and electrophilicity calculations showed that the gas adsorbed complexes are rigid and therefore robust as gas storage materials.

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MPMC and MCMD: Free High‐Performance Simulation Software for Atomistic Systems

Franz

Belof

McLaughlin

et al. 2019

Advcd Theory and Sims

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Advancements in parallel computing and hardware have allowed computational exploration of chemical systems of interest with unprecendented accuracy and efficiency. The typical development of molecular simulation software is initially inspired by a particular scientific inquiry. The softwares presented herein, MPMC (Massively Parallel Monte Carlo) and MCMD (Monte Carlo/Molecular Dynamics) were born out of a pursuit to simulate condensed phase physical and chemical interactions in porous materials. MPMC first began in 2005 and has been used for dozens of published results in the literature but has not yet been introduced in a standalone paper. MCMD is a more recent expansion and re‐write with some published work, focused on adding molecular dynamics algorithms for transport and other time‐dependent properties of chemical systems. Each software functions as a standalone with some unique and other overlapping features. A driving aim of this work is to consider periodic, long‐range polarization effects in classical simulation, and both codes are optimized to perform such calculations. Sample results will be presented which highlight methodically that inclusion of explicit polarization produces simulation results with predictive power which in general are in greater agreement with experiment than non‐polarizable analogous simulations.

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Theoretical Investigations of CO₂ and CH₄ Sorption in an Interpenetrated Diamondoid Metal–Organic Material

Cited by 36 publications

References 60 publications

Understanding Hydrogen Sorption in In-soc-MOF: A Charged Metal-Organic Framework with Open-Metal Sites, Narrow Channels, and Counterions

Understanding Hydrogen Sorption in In-soc-MOF: A Charged Metal-Organic Framework with Open-Metal Sites, Narrow Channels, and Counterions

Probing the bent bonds in cyclopropane systems for gas storage and separation process: A computational study

MPMC and MCMD: Free High‐Performance Simulation Software for Atomistic Systems

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Theoretical Investigations of CO2 and CH4 Sorption in an Interpenetrated Diamondoid Metal–Organic Material

Cited by 36 publications

References 60 publications

Understanding Hydrogen Sorption in In-soc-MOF: A Charged Metal-Organic Framework with Open-Metal Sites, Narrow Channels, and Counterions

Understanding Hydrogen Sorption in In-soc-MOF: A Charged Metal-Organic Framework with Open-Metal Sites, Narrow Channels, and Counterions

Probing the bent bonds in cyclopropane systems for gas storage and separation process: A computational study

MPMC and MCMD: Free High‐Performance Simulation Software for Atomistic Systems

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Product

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Theoretical Investigations of CO₂ and CH₄ Sorption in an Interpenetrated Diamondoid Metal–Organic Material