Fig. 5: Correlation of defect generation, growth, and collapse with gas uptake.

a N₂ isotherms at 77 K of the defect-free sample used as a reference (linket to metal ratio (L/M) = 1.5, temperature (T) = 180 °C) and defective samples synthesized at 120 °C for varying linker concentrations, the horizontal axis is the relative pressure (P/P^o). Adsorption and desorption branches are represented by filled and empty symbols. Dotted lines correspond to the expected values for ideal fcu and reo topologies calculated with Zeo^{++ 38,40,52}. b Pore size distribution plots calculated with a NLDFT kernel for the experimental isotherms and normalized to the total accessible volume so that ∫(dV/dW) dW = 1 for all distributions. Pore width (W) values for the tetrahedral (orange) and octahedral (yellow) cavities intrinsic to the fcu framework and the bigger cavities (purple) formed in reo topologies from missing cluster vacancies have been added as a reference. Crystallographic views of c) fcu and d) reo frameworks along the [100] direction for identification of these cavities. Atoms are represented in color: zirconium (blue polyhedron), oxygen (red), carbon (gray sticks).