Modulated self-assembly of an interpenetrated MIL-53 Sc metal–organic framework with excellent volumetric H2 storage and working capacity

To achieve optimal performance in gas storage and delivery applications, metal–organic frameworks (MOFs) must combine high gravimetric and volumetric capacities. One potential route to balancing high pore volume with suitable crystal density is interpenetration, where identical nets sit within the void space of one another. Herein, we report an interpenetrated MIL-53 topology MOF, named GUF-1, where one-dimensional Sc(μ2-OH) chains are connected by 4,4′-(ethyne-1,2-diyl)dibenzoate linkers into a material that is an unusual example of an interpenetrated MOF with a rod-like secondary building unit. A combination of modulated self-assembly and grand canonical Monte Carlo simulations are used to optimise the porosity of GUF-1; H2 adsorption isotherms reveal a moderately high Qst for H2 of 7.6 kJ/mol and a working capacity of 41 g/L in a temperature–pressure swing system, which is comparable to benchmark MOFs. These results show that interpenetration is a potentially viable route to high-performance gas storage materials comprised of relatively simple building blocks. [Display omitted] •An unusual example of an interpenetrated metal–organic framework (MOF) connected by a one-dimensional chain secondary building unit.•Optimisation of MOF porosity through a dual modulation strategy.•Characterisation of flexibility by a combination of experiments and grand canonical Monte Carlo simulations.•A high working capacity for H2 of 41 g/L in a temperature–pressure swing system.