Post-hybridization of MIL-101(Cr) with graphene oxide enhances its hydrogen storage and release capacities

Abstract

Hydrogen (H₂) is a clean and high-energy carrier; however, its low volumetric energy density remains a major barrier to practical storage and transport. This study demonstrates that the hybridization of MIL-101(Cr) with graphene oxide (GO) effectively enhances H₂ storage and release capacities. The integration of GO, with a density of 450 kg m^-3, into MIL-101(Cr), a highly porous metal-organic framework (A_BET ≥ 3,500 m² g^-1, V_pore ≥ 2.0 cm³ g^-1 and 259 kg m^-3 of density) was investigated through a post-synthetic hybridization strategy, leading to increased ultra-microporosity and enhanced density of the resulting hybrids. Although GO incorporation led to a reduction in gravimetric (wt.%) H₂ storage at 77 K and 100 bar, ranging from 3% to 36% as GO content increased, it significantly improved H₂ uptake at 273 K and 100 bar. The hybrid with 1 wt.% GO exhibited the most notable enhancement, achieving a 40% increase in gravimetric storage capacity (273 K, 100 bar) compared to pure MIL-101(Cr). This hybrid also demonstrated superior volumetric performance, reaching a 6% increase both in total H₂ storage, 35.8 kg m^-3 (77 K, 100 bar), and deliverable capacity, 34.2 kg m^-3, under practical operating conditions (i.e., charging: 77 K and 100 bar; discharging: 160 K and 5 bar). These findings highlight the dual role of GO: densifying the composite while potentially introducing ultramicroporosity, particularly effective at elevated temperatures, offering a promising pathway toward practical, scalable, and efficient hydrogen storage systems.

Keywords

MOF / hydrogen storage / adsorption / GO / MOF/GO hybrids

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