Room-temperature hydrogen storage performance of metal-organic framework/graphene oxide composites by molecular simulations

Metal-organic framework/graphene oxide (MOF/GO) composites have been regarded as potential room-temperature hydrogen storage materials recently. In this work, the influence of MOF structural properties, GO functional group contents and different amounts of doped lithium (Li+) on hydrogen storage performance of different MOF/GO composites were investigated by grand canonical Monte Carlo (GCMC) simulations. It is found that MOF/GO composites based on small-pore MOFs exhibit enhanced hydrogen storage capacity, whereas MOF/GO based on large-pore MOFs show decreased hydrogen storage capacity, which can be ascribed to the novel pores at MOF/GO interface that favors the enhanced hydrogen storage performance due to the increased pore volume/surface area. By integrating the small-pore MOF-1 with GO, the hydrogen storage capacity was enhanced from 9.88 mg/go up to 11.48 mg/g. However, the interfacial pores are smaller compared with those in large-pore MOFs, resulting in significantly reduced pore volume/surface area as well as hydrogen storage capacities of large-pore MOF/GO composite. Moreover, with the increased contents of hydroxyl, epoxy groups as well as carboxyl group modification, the pore volumes and specific surface areas of MOF/GO are decreased, resulting in reduced hydrogen storage performance. Furthermore, the room-temperature hydrogen storage capacities of Li+ doped MOF/GO was improved with increased Li+ at low loading and decrease with the increased Li+ amounts at high loading. This is due to that the introduced Li+ effectively increases the accessible hydrogen adsorption sites at low Li+ loading, which eventually favors the hydrogen adsorption capacity. However, high Li+ loading causes ion aggregation that reduces the accessible hydrogen adsorption sites, leading to decreased hydrogen storage capacities. MOF-5/GO composites with moderate Li+ doping achieved the optimum hydrogen storage capacities of approximately 29 mg/g.