Tuning Hydrogen Sorption Properties of Metal–Organic Frameworks by Postsynthetic Covalent Modification

Postsynthetic modification is presented as a means to tune the hydrogen adsorption properties of a series of metal–organic frameworks (MOFs). IRMOF‐3 (isoreticular metal–organic framework), UMCM‐1‐NH₂ (University of Michigan crystalline material), and DMOF‐1‐NH₂ (DABCO metal–organic framework) have been covalently modified with a series of anhydrides or isocyanates and the hydrogen sorption properties have been studied. Both the storage capacities and isosteric heats of adsorption clearly show that covalent postsynthetic modification can significantly enhance the sorption affinity of MOFs with hydrogen and in some cases increase both gravimetric and volumetric uptake of the gas as much as 40 %. The significance of the present study is illustrated by: 1) the nature of the substituents introduced by postsynthetic modification result in different effects on the binding of hydrogen; 2) the covalent postsynthetic modification approach allows for systematic modulation of hydrogen sorption properties; and 3) the ease of postsynthetic modification of MOFs allows a direct evaluation of the interplay between MOF structure, hydrogen uptake, and heat of adsorption. The findings presented herein show that postsynthetic modification is a powerful method to manipulate and better understand the gas sorption properties of MOFs.