Correction to “Catechol-Ligated Transition Metals: A Quantum Chemical Study on a Promising System for Gas Separation”

Stoneburner, Samuel J.; Livermore, Vanessa; McGreal, Meghan E.; Yu, Decai; Vogiatzis, Konstantinos D.; Snurr, Randall Q.; Gagliardi, Laura

doi:10.1021/acs.jpcc.7b08653

Cited by 1 publication

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“…Stoneburner et al previously reported that M06 gives accurate results for other gases, including water, binding to metal catecholates. 43 We tested several basis sets using the M06 functional (Figure S2). We find that all four basis sets are in close agreement for the binding energy of MeBr on Mg, Mn, and Pt.…”

Section: ■ Computational Methodsmentioning

confidence: 99%

“…We do note that MeBr binding energies using the M06 DFT functional (paired with the 6-311+G(d,p) basis set and the LANL2DZ ECP) are consistently lower (stronger) compared to B3LYP (paired with the same basis set and ECP) by an average of 16 kJ/mol and are lower than PBE for Mg, Mn, Zn, and Cd (but not Pt) by an average of 16 kJ/mol. Stoneburner et al previously reported that M06 gives accurate results for other gases, including water, binding to metal catecholates . We tested several basis sets using the M06 functional (Figure S2).…”

Section: Computational Methodsmentioning

confidence: 99%

“…The geometry of the catecholate leaves the metal site open and easily accessible by the adsorbate. Also, they can be incorporated into MOFs and porous organic polymers and can be made from a variety of metals. − The ionic character, electron affinity, and orbital occupancy of the metal atom in a catecholate greatly influence the binding strength and selectivity for adsorbing the target molecule. ,,− To our knowledge, there is no systematic study of MeBr binding on a wide range of metals currently in the literature.…”

Section: Introductionmentioning

confidence: 99%

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Competitive Adsorption of Methyl Bromide and Water on Metal Catecholates: Insights from Density Functional Theory

Bobbitt

Snurr

2018

Ind. Eng. Chem. Res.

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Density functional theory was used to study the interaction of methyl bromide (MeBr) and water with a large number metal catecholates. Differences in the binding mechanism of MeBr and water result in differences in the adsorption selectivity of the alkaline earth, early transition, and late transition metals. The binding of water is primarily driven by electrostatic attraction between the water oxygen atom and the metal, which means the alkaline earth and early transition metals heavily favor water over MeBr. For the more electronegative late transition metals, MeBr donates a significant amount of electron density to the metal, which dominates over the electrostatic binding effect. These metals favor MeBr over water, based on single molecule adsorption calculations. However, calculations of simultaneous adsorption of water and MeBr indicate that MeBr adsorption on late transition metals such as Pt and Au is detrimentally affected by the presence of water, while MeBr adsorption on Ca is more resistant to the presence of humidity. Therefore, despite lower single-component selectivity for MeBr, Ca and other alkaline earth metals might offer advantages for MeBr adsorption applications in humid environments. Also, in the case of four metals (Sc, Y, Hf, and Ta), MeBr is predicted to dissociate and bind separately to the metal as a Br atom and a methyl group, resulting in a very favorable binding energy (>275 kJ/mol).

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Section: ■ Computational Methodsmentioning

confidence: 99%

Section: Computational Methodsmentioning

confidence: 99%