Ambient-Temperature Hydrogen Storage via Vanadium(II)-Dihydrogen Complexation in a Metal-Organic Framework

The widespread implementation of H-2 as a fuel is currently hindered by the high pressures or cryogenic temperatures required to achieve reasonable storage densities. In contrast, the realization of materials that strongly and reversibly adsorb hydrogen at ambient temperatures and moderate pressures could transform the transportation sector and expand adoption of fuel cells in other applications. To date, however, no adsorbent has been identified that exhibits a binding enthalpy within the optimal range of -15 to -25 kJ/mol for ambient-temperature hydrogen storage. Here, we report the hydrogen adsorption properties of the metal-organic framework (MOF) V2Cl2.8(btdd) (H(2)btdd, bis(H-1-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), which features exposed vanadium(II) sites capable of backbonding with weak pi acids. Significantly, gas adsorption data reveal that this material binds H-2 with an enthalpy of -21 kJ/mol. This binding energy enables usable hydrogen capacities that exceed that of compressed storage under the same operating conditions. The Kubas-type vanadium(II)-dihydrogen complexation is characterized by a combination of techniques. From powder neutron diffraction data, a V-D-2(centroid) distance of 1.966(8) angstrom is obtained, the shortest yet reported for a MOF. Using in situ infrared spectroscopy, the H-H stretch was identified, and it displays a red shift of 242 cm(-1). Electronic structure calculations show that a main contribution to bonding stems from the interaction between the vanadium d(pi) and H-2 sigma* orbital. Ultimately, the pursuit of MOFs containing high densities of weakly pi-basic metal sites may enable storage capacities under ambient conditions that far surpass those accessible with compressed gas storage.

Automated summary

The widespread implementation of hydrogen as a fuel is hindered by technical challenges, but researchers have discovered a metal-organic framework material with the potential to adsorb hydrogen, enabling high-density storage at ambient temperatures, which opens up new possibilities for the application of hydrogen energy.