Defects in metal–organic frameworks: a compromise between adsorption and stability?

Abstract

Defect engineering has arisen as a promising approach to tune and optimise the adsorptive performance of metal–organic frameworks. However, the balance between enhanced adsorption and structural stability remains an open question. Here both CO₂ adsorption capacity and mechanical stability are calculated for the zirconium-based UiO-66, which is subject to systematic variations of defect scenarios. Modulator-dependence, defect concentration and heterogeneity are explored in isolation. Mechanical stability is shown to be compromised at high pressures where uptake is enhanced with an increase in defect concentration. Nonetheless this reduction in stability is minimised for reo type defects and defects with trifluoroacetate substitution. Finally, heterogeneity and auxeticity may also play a role in overcoming the compromise between adsorption and stability.