Crystal engineering of porous coordination networks to enable separation of C2 hydrocarbons

Crystal engineering, the field of chemistry that studies the design, properties, and applications of crystals, is exemplified by the emergence over the past thirty years of porous coordination networks (PCNs), including metal-organic frameworks (MOFs) and hybrid coordination networks (HCNs). PCNs have now come of age thanks to their amenability to design from first principles and how this in turn can result in new materials with task-specific features. Herein, we focus upon how control over the pore chemistry and pore size of PCNs has been leveraged to create a new generation of physisorbents for efficient purification of light hydrocarbons (LHs). The impetus for this research comes from the need to address LH purification processes based upon cryogenic separation, distillation, chemisorption or solvent extraction, each of which is energy intensive. Adsorptive separation by physisorbents (in general) and PCNs (in particular) can offer two advantages over these existing approaches: improved energy efficiency; lower plant size/cost. Unfortunately, most existing physisorbents suffer from low uptake and/or poor sorbate selectivity and are therefore unsuitable for trace separations of LHs including the high volume C2 LHs (C₂H_x, x = 2, 4, 6). This situation is rapidly changing thanks to PCN sorbents that have set new performance benchmarks for several C2 separations. Herein, we review and analyse PCN sorbents with respect to the supramolecular chemistry of sorbent-sorbate binding and detail the crystal engineering approaches that have enabled the exquisite control over pore size and pore chemistry that affords highly selective binding sites. Whereas the structure-function relationships that have emerged offer important design principles, several development roadblocks remain to be overcome.