MultiBinding Sites United in Covalent-Organic Frameworks (MSUCOF) for H2 Storage and Delivery at Room Temperature

The storage of hydrogen gas (\ce{H2}) has presented a significant challenge that has hindered its use as a fuel source for transportation. To meet the Department of Energy's ambitious goals of achieving 50 g L$^{-1}$ volumetric and 6.5 wt \% gravimetric uptake targets, materials-based approaches are essential. Designing materials that can efficiently store hydrogen gas requires careful tuning of the interactions between the gaseous \ce{H2} and the surface of the material. Metal-Organic Frameworks (MOFs) and Covalent-Organic Frameworks (COFs) have emerged as promising materials due to their exceptionally high surface areas and tunable structures that can improve gas-framework interactions. However, weak binding enthalpies have limited the success of many current candidates, which fail to achieve even 10 g L$^{-1}$ volumetric uptake at ambient temperatures. To overcome this challenge, We utilized quantum mechanical (QM) based force fields (FF) to investigate the uptake and binding enthalpies of 3 linkers chelated with 7 different transition metals (TM), including both precious metals (Pd and Pt) and first row TM (Co, Cu, Fe, Ni, Mn), to design 24 different COFs in-silico. By applying QM-based FF with grand canonical Monte Carlo (GCMC) from 0-700 bar and 298 K, We demonstrated that Co-, Ni-, Mn-, Fe-, Pd-, and Pt-based MSUCOFs can already achieve the Department of Energy's hydrogen storage targets for 2025. Surprisingly, the COFs that incorporated the more affordable and abundant first-row TM often outperformed the precious metals. This promising development brings us one step closer to realizing a hydrogen-based energy economy.