A genetic algorithm was used to accelerate the computational discovery of new nanoporous materials for capturing CO2.

Computational high-throughput screening was carried out to assess a large number of experimentally reported metal−organic frameworks (MOFs) and zeolites for their utility in hexane isomer separation. Through the work, we identified many MOFs and zeolites with high selectivity (S L+M > 10) for the group of n-hexane, 2-methylpentane, and 3methylpentane (linear and monobranched isomers) versus 2,2dimethylbutane and 2,3-dimethylbutane (dibranched isomers). This group of selective sorbents includes VICDOC (Fe 2 (BDP) 3 ), a MOF with triangular pores that is known to exhibit high isomer selectivity and capacity. For three of these structures, the adsorption isotherms for a 10-component mixture of hexane and heptane isomers were calculated. Subsequent simulations of column breakthrough curves showed that the DEYVUA MOF exhibits a longer process cycle time than VICDOC MOF or MRE zeolite, which are previously reported, high-performing materials, illustrating the importance of capacity in designing MOFs for practical applications. Among the identified candidates, we synthesized and characterized a MOF in a new copper form with high predicted adsorbent capacity (q L+M > 1.2 mol/L) and moderately high selectivity (S L+M ≈ 10). Finally, we examined the role of pore shape in hexane isomer separations, especially of triangular-shaped pores. We show through the potential energy surface and three-dimensional siting analyses that linear alkanes do not populate the corners of narrow triangular channels and that structures with nontriangular pores can efficiently separate hexane isomers. Detailed thermodynamic analysis illustrates how differences in the free energy of adsorption contribute to shapeselective separation in nanoporous materials.

CO2 capture is essential for reducing the carbon footprint of coal-fired power plants. Here we show, both experimentally and computationally, a new design strategy for capturing CO2 in nanoporous adsorbents. The approach involves 'complementary organic motifs' (COMs), which have a precise alignment of charge densities that is complementary to the CO2 quadrupole. Two promising COMs were post-synthetically incorporated into a robust metal-organic framework (MOF) material using solvent-assisted ligand incorporation (SALI). We demonstrate that these COM-functionalized MOFs exhibit high capacity and selectivity for CO2 relative to other reported motifs.