Microscopic insight into the shaping of MOFs and its impact on CO capture performance.

The traditional synthesis method produces microcrystalline powdered MOFs, which prevents direct implementation in real-world applications which demand strict control of shape, morphology and physical properties. Therefore, shaping of MOFs the use of binders is of paramount interest for their practical use in gas adsorption/separation, catalysis, sensors, . However, so far, the binders have been mostly selected by trial-and-error without anticipating the adhesion between the MOF and binder components to ensure the processability of homogeneous and mechanically stable shaped MOFs and the impact of the shaping on the intrinsic properties of the MOFs has been overlooked. Herein, we deliver a first systematic multiscale computational exploration of MOF/binder composites by selecting CALF-20, a prototypical MOF for real application in the field of CO capture, and a series of binders that cover a rather broad spectrum of properties in terms of rigidity/flexibility, porosity, and chemical functionality. The adhesion between the two components and hence the effectiveness of the shaping as well as the impact of the overall porosity of the CALF-20/binder on the CO/N selectivity, CO sorption capacity and kinetics was analyzed. Shaping of CALF-20 by carboxymethyl cellulose was predicted to enable a fair compromise between excellent adhesion between the two components, whilst maintaining high CO/N selectivity, large CO uptake and CO transport as fast as in the CALF-20. This multiscale computational tool paves the way towards the selection of an appropriate binder to achieve an optimum shaping of a given MOF in terms of processability whilst maintaining its high level of performance.