Computational Selection of High-Performing Covalent Organic Frameworks for Adsorption and Membrane-Based CO2/H2 Separation

Covalent organic frameworks (COFs) have high potential in gas separation technologies because of their porous structures, large surface areas, and good stabilities. The number of synthesized COFs already reached several hundreds, but only a handful of materials were tested as adsorbents and/or membranes. We used a high-throughput computational screening approach to uncover adsorption-based and membrane-based CO 2 /H 2 separation potentials of 288 COFs, representing the highest number of experimentally synthesized COFs studied to date for precombustion CO 2 capture. Grand canonical Monte Carlo (GCMC) simulations were performed to assess CO 2 /H 2 mixture separation performances of COFs for five different cyclic adsorption processes: pressure swing adsorption, vacuum swing adsorption, temperature swing adsorption (TSA), pressure-temperature swing adsorption (PTSA), and vacuum-temperature swing adsorption (VTSA). The results showed that many COFs outperform traditional zeolites in terms of CO 2 selectivities and working capacities and PTSA is the best process leading to the highest adsorbent performance scores. Combining GCMC and molecular dynamics (MD) simulations, CO 2 and H 2 permeabilities and selectivities of COF membranes were calculated. The majority of COF membranes surpass Robeson's upper bound because of their higher H 2 permeabilities compared to polymers, indicating that the usage of COFs has enormous potential to replace current materials in membrane-based H 2 /CO 2 separation processes. Performance analysis based on the structural properties showed that COFs with narrow pores [the largest cavity diameter (LCD) < 15 Å] and low porosities (ϕ < 0.75) are the top adsorbents for selective separation of CO 2 from H 2 , whereas materials with large pores (LCD > 20 Å) and high porosities (ϕ > 0.85) are generally the best COF membranes for selective separation of H 2 from CO 2 . These results will help to speed up the engineering of new COFs with desired structural properties to achieve high-performance CO 2 /H 2 separations.