Impact of Metal and Anion Substitutions on the Hydrogen Storage Properties of M-BTT Metal–Organic Frameworks

Microporous metal − organic frameworks are a class of materials being vigorously investigated for mobile hydrogen storage applications. For high-pressure storage at ambient temperatures, the M 3 [(M 4 Cl) 3 (BTT) 8 ] 2 (M-BTT; BTT 3 − = 1,3,5-benzenetristetrazolate) series of frameworks are of particular interest due to the high density of exposed metal cation sites on the pore surface. These sites give enhanced zero-coverage isosteric heats of adsorption (Q st ) approaching the optimal value for ambient storage applications. However, the Q st parameter provides only a limited insight into the thermodynamics of the individual adsorption sites, the tuning of which is paramount for optimizing the storage performance. Here, we begin by performing variable-temperature infrared spectroscopy studies of Mn-, Fe-, and Cu-BTT, allowing the thermodynamics of H2 adsorption to be probed experimentally. This is complemented by a detailed DFT study, in which molecular fragments representing the metal clusters within the extended solid are simulated to obtain a more thorough description of the structural and thermodynamic aspects of H2 adsorption at the strongest binding sites. Then, the e ff ect of substitutions at the metal cluster (metal ion and anion within the tetranuclear cluster) is discussed, showing that the con fi guration of this unit indeed plays an important role in determining the affinity of the framework toward H2. Interestingly, the theoretical study has identi fi ed that the Zn-based analogs would be expected to facilitate enhanced adsorption profiles over the compounds synthesized experimentally, highlighting theimportance of a combined experimental and theoretical approach to the design and synthesis of new frameworks for H2 storage applications.