Force Field Development from Periodic Density Functional Theory Calculations for Gas Separation Applications Using Metal–Organic Frameworks

Abstract

We present accurate force fields developed from density functional theory (DFT) calculations with periodic boundary conditions for use in molecular simulations involving M<sub>2</sub>(dobdc) (M-MOF-74; dobdc<sup>4–</sup> = 2,5-dioxidobenzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Zn) and frameworks of similar topology. In these systems, conventional force fields fail to accurately model gas adsorption due to the strongly binding open-metal sites. The DFT-derived force fields predict the adsorption of CO<sub>2</sub>, H<sub>2</sub>O, and CH<sub>4</sub> inside these frameworks much more accurately than other common force fields. We show that these force fields can also be used for M<sub>2</sub>(dobpdc) (dobpdc<sup>4–</sup> = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), an extended version of MOF-74, and thus are a promising alternative to common force fields for studying materials similar to MOF-74 for carbon capture applications. Furthermore, it is anticipated that the approach can be applied to other metal–organic framework topologies to obtain force fields for different systems. We have used this force field to study the effect of contaminants such as H<sub>2</sub>O and N<sub>2</sub> upon these materials’ performance for the separation of CO<sub>2</sub> from the emissions of natural gas reservoirs and coal-fired power plants. Specifically, mixture adsorption isotherms calculated with these DFT-derived force fields showed a significant reduction in the uptake of many gas components in the presence of even trace amounts of H<sub>2</sub>O vapor. The extent to which the various gases are affected by the concentration of H<sub>2</sub>O in the reservoir is quantitatively different for the different frameworks and is related to their heats of adsorption. Additionally, significant increases in CO<sub>2</sub> selectivities over CH<sub>4</sub> and N<sub>2</sub> are observed as the temperature of the systems is lowered.