Record High Hydrogen Storage Capacity in the Metal–Organic Framework Ni₂(m-dobdc) at Near-Ambient Temperatures

Hydrogen holds promise as a clean alternative automobile fuel, but its on-board storage presents significant challenges due to the low temperatures and/or high pressures required to achieve a sufficient energy density. The opportunity to significantly reduce the required pressure for high density H₂ storage persists for metal-organic frameworks due to their modular structures and large internal surface areas. The measurement of H₂ adsorption in such materials under conditions most relevant to on-board storage is crucial to understanding how these materials would perform in actual applications, although such data have to date been lacking. In the present work, the metal-organic frameworks M₂(m-dobdc) (M = Co, Ni; m-dobdc⁴⁻ = 4,6-dioxido-1,3-benzenedicarboxylate) and the isomeric frameworks M₂(dobdc) (M = Co, Ni; dobdc⁴⁻ = 1,4-dioxido-1,3-benzenedicarboxylate), which are known to have open metal cation sites that strongly interact with H₂, were evaluated for their usable volumetric H₂ storage capacities over a range of near-ambient temperatures relevant to on-board storage. Based upon adsorption isotherm data, Ni₂(m-dobdc) was found to be the top-performing physisorptive storage material with a usable volumetric capacity between 100 and 5 bar of 11.0 g/L at 25 °C and 23.0 g/L with a temperature swing between -75 and 25 °C. Additional neutron diffraction and infrared spectroscopy experiments performed with in situ dosing of D₂ or H₂ were used to probe the hydrogen storage properties of these materials under the relevant conditions. The results provide benchmark characteristics for comparison with future attempts to achieve improved adsorbents for mobile hydrogen storage applications.