CO<sub>2</sub>Adsorption in Fe<sub>2</sub>(dobdc): A Classical Force Field Parameterized from Quantum Mechanical Calculations

Borycz, Joshua; Lin, Li‐Chiang; Bloch, Eric D.; Kim, Jihan; Dzubak, Allison L.; Maurice, Rémi; Semrouni, David; Lee, Kyuho; Smit, Berend; Gagliardi, Laura

doi:10.1021/jp500313j

Cited by 46 publications

(74 citation statements)

References 68 publications

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“…In a subsequent work, Borycz et al 21 have used a similar approach to predict CO2 adsorption in Fe-MOF-74. Chen et al 22 have also successfully derived a force field for the adsorption of CO2 and CH4 by using a dispersion-corrected double-hybrid functional (B2PLYP-D2).…”

Section: Introductionmentioning

confidence: 99%

“…Similar clusters have been used previously to study the adsorption of CO2 and N2 in Mg2(dobdc) 17 and Fe2(dobdc). 21 A more detailed description of the cluster design can be found in ref. 17 Complete-active space self-consistent field (CASSCF) 33 calculations were performed to identify the ground spin states of the unsaturated metal ions.…”

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confidence: 99%

“…The basis set superposition error (BSSE) was corrected in both sets of calculations using the counterpoise correction 44 21 showing that the effect of replacing the non-central atoms with Zn, in similar Fe-MOF-74 clusters, had a negligible effect on the MOF-CO2 interaction energy.…”

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confidence: 99%

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Ab Initio Derived Force Fields for Predicting CO₂ Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)

Haldoupis¹,

Borycz²,

Shi³

et al. 2015

J. Phys. Chem. C

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107

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Metal-organic frameworks (MOFs) are versatile nanoporous materials that have gained significant interest as low heat capacity, high selectivity sorbents for CO2 capture applications. Large-scale atomistic simulations for identifying high-performance MOFs are possible, but are limited to systems for which existing molecular mechanics force fields describe the interactions between the guest and framework atoms with sufficient accuracy.However, standard force fields are not applicable to cases involving coordinatively unsaturated metal centers that can strongly bind specific sorbate molecules. It has been previously shown that improved force fields can be derived from quantum mechanical calculations. In this work, we derived force fields for an isostructural series of MOFs, M-MOF-74, where M = Mn, Co, Ni, and Cu, from first principles. Monte Carlo calculations in the Gibbs ensemble were used to calculate the CO2 isotherms in order to assess the quality of the derived force field parameters and to determine a generally applicable procedure for obtaining a reliable force field for a targeted MOF and adsorbate system. The computed CO2 adsorption isotherms for the different M-MOF-74 members agree with experimental measurements at low loading and show that Ni-MOF-74 possesses the highest affinity towards CO2 and Cu-MOF-74 the weakest. In addition, we explored the source of open metal site and pore inaccessibility in these materials and quantified its impact on adsorption, especially the discrepancies often observed between experiments and simulations at high loadings.

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

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Ab Initio Derived Force Fields for Predicting CO₂ Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)

Haldoupis¹,

Borycz²,

Shi³

et al. 2015

J. Phys. Chem. C

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107

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“…It can mean choosing an entirely altogether functional form for the metal-adsorbate interactions, or even a numerical description based on the energy profile as a function of adsorbate-metal center distance. There are several examples of force field optimization for open metal site MOFs in the literature, including the cases of: hydrogen in HKUST-1; [246] water in copper-based MOFs; [255] carbon dioxide and water in Mg-MOF-74 [256] and Zn-MOF-74;[257] CO 2 adsorption in Fe 2 (dobdc); [258] etc. We detail here by way of illustration the procedure followed by Chen et al [249] for the ab initio parameterization of a force field describing the adsorption of CO 2 in CPO-27-Mg.…”

Section: Beyond Classical Force Fields: Open Metal Sites and Chemisormentioning

confidence: 99%

Computational characterization and prediction of metal–organic framework properties

Coudert

Fuchs

2016

Coordination Chemistry Reviews

240

203

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In this introductory review, we give an overview of the computational chemistry methods commonly used in the field of metal-organic frameworks (MOFs), to describe or predict the structures themselves and characterize their various properties, either at the quantum chemical level or through classical molecular simulation. We discuss the methods for the prediction of crystal structures, geometrical properties and large-scale screening of hypothetical MOFs, as well as their thermal and mechanical properties. A separate section deals with the simulation of adsorption of fluids and fluid mixtures in MOFs.

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“…[ 54 ] Furthermore, all structural analogs within the M 2 (dobdc) family are of high crystalline quality, allowing for detailed studies of structure-property relationships and providing an experimental platform to test how accurately developing force fi elds can describe the guest interaction in slightly varying chemical environments. [ 55,56 ] Recent studies on this framework encompass a wide range of experimental and theoretical methodologies utilized to characterize interactions with various guests in the M 2 (dobdc) compound family ( Figure 3 ). [ 57 ] While this is certainly not the only important MOF, it is highly prominent and has been the focus of many theoretical and experimental studies alike and consequently was chosen to be our focus within the context of this article.…”

Section: Research Newsmentioning

confidence: 99%

Understanding Small‐Molecule Interactions in Metal–Organic Frameworks: Coupling Experiment with Theory

et al. 2015

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are intensive scientifi c efforts focused on the development of new physical adsorbents that might enable more energetically favorable gas separation, relative to traditional distillation or absorption processes. This feat is not easy, as the differences in the molecules of interest, such as CO 2 and N 2 -the main components in a postcombustion fl ue gas, are minimal. [ 2,3 ] As such, these separations require tailor-made adsorbent materials with molecule-specifi c chemical interactions on their internal surface. [ 4,5 ] Metal-organic frameworks (MOFs) are a particularly attractive class of porous adsorbents that are under intense investigation for gas separation due to their unmatched structural versatility. Many stable, 3D frameworks that offer unprecedented internal surface areas and the selective adsorption of a wide range of small guest molecules have been discovered. [ 6 ] The molecular nature of the organic ligand in an MOF provides a convenient modular approach to their synthesis and facile chemical tunability, creating a surge towards the directed design of new materials ( Figure 1 ). [7][8][9] Through judicious selection of the ligand and metal, which control pore size/shape and MOF-adsorbate interactions, MOF uptake properties, Metal-organic frameworks (MOFs) have gained much attention as nextgeneration porous media for various applications, especially gas separation/ storage, and catalysis. New MOFs are regularly reported; however, to develop better materials in a timely manner for specifi c applications, the interactions between guest molecules and the internal surface of the framework must fi rst be understood. A combined experimental and theoretical approach is presented, which proves essential for the elucidation of small-molecule interactions in a model MOF system known as M 2 (dobdc) (dobdc 4− = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, or Zn), a material whose adsorption properties can be readily tuned via chemical substitution. It is additionally shown that the study of extensive families like this one can provide a platform to test the effi cacy and accuracy of developing computational methodologies in slightly varying chemical environments, a task that is necessary for their evolution into viable, robust tools for screening large numbers of materials.

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CO₂Adsorption in Fe₂(dobdc): A Classical Force Field Parameterized from Quantum Mechanical Calculations

Cited by 46 publications

References 68 publications

Ab Initio Derived Force Fields for Predicting CO₂ Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)

Ab Initio Derived Force Fields for Predicting CO₂ Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)

Computational characterization and prediction of metal–organic framework properties

Understanding Small‐Molecule Interactions in Metal–Organic Frameworks: Coupling Experiment with Theory

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CO2Adsorption in Fe2(dobdc): A Classical Force Field Parameterized from Quantum Mechanical Calculations

Cited by 46 publications

References 68 publications

Ab Initio Derived Force Fields for Predicting CO2 Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)

Ab Initio Derived Force Fields for Predicting CO2 Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)

Computational characterization and prediction of metal–organic framework properties

Understanding Small‐Molecule Interactions in Metal–Organic Frameworks: Coupling Experiment with Theory

Contact Info

Product

Resources

About

CO₂Adsorption in Fe₂(dobdc): A Classical Force Field Parameterized from Quantum Mechanical Calculations

Ab Initio Derived Force Fields for Predicting CO₂ Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)

Ab Initio Derived Force Fields for Predicting CO₂ Adsorption and Accessibility of Metal Sites in the Metal–Organic Frameworks M-MOF-74 (M = Mn, Co, Ni, Cu)