Ferrocene-functionalized covalent organic framework exceeding the ultimate hydrogen storage targets: a first-principles multiscale computational study

Abstract The development of efficient hydrogen storage materials is crucial for advancing the hydrogen economy and meeting the U.S. Department of Energy’s targets of 6.5 wt% and 50 g L −1 for automotive applications. We present a computational study of ferrocene-functionalized covalent organic frameworks (COFs) for hydrogen storage. Following the M ulti-binding S ites U nited in C ovalent- O rganic F ramework (MSUCOF) approach, we introduce MSUCOF-4-FeCp, designed by incorporating ferrocene (FeCp 2 ) moieties into IRCOF-102. Notably, it achieves exceptional performance with total gravimetric and volumetric uptakes of 18.0 wt% and 72.6 g L −1 at 298 K and 700 bar. The material exhibits optimal binding energies (15–20 kJ⋅mol −1 ) ensuring both high total uptake and a high working capacity. This work establishes ferrocene functionalization as a cost-effective alternative to precious metal incorporation in COFs.