Birch reduction of few-layer graphene samples gives rise to hydrogenated samples containing up to 5 wt % of hydrogen. Spectroscopic studies reveal the presence of sp 3 C-H bonds in the hydrogenated graphenes. They, however, decompose readily on heating to 500°C or on irradiation with UV or laser radiation releasing all the hydrogen, thereby demonstrating the possible use of few-layer graphene for chemical storage of hydrogen. First-principles calculations throw light on the mechanism of dehydrogenation that appears to involve a significant reconstruction and relaxation of the lattice.hydrogen storage | reversible hydrogenation S torage of hydrogen in a suitable solid matrix is a major challenge facing the scientific community (1). Some time ago carbon nanotubes were suggested to be useful for storing hydrogen, but only ∼3 wt % storage has since been achieved (2-4). It has been shown that reaction of single-layer graphene with hydrogen atoms generates sp 3 C-H bonds on the basal plane and the reduced material gets dehydrogenated on photothermal heating (5). Reaction of atomic hydrogen with graphene produces hydrogenated graphene giving rise to changes in electronic and phonon properties (6). Through such hydrogen loading, a tunable band gap can be induced in graphene (7). The nature of hydrogen in the hydrogenated samples or the amount of hydrogen uptake by graphene has not been delineated. It has been suggested that hydrogenation of graphene may be more feasible with multilayer graphene than that with single-layer graphene (8). In the light of these reports, we have carried out detailed studies on the reduction of few-layer graphene samples prepared by two independent methods (9, 10) and examined the structure and stability of the hydrogenated products. We have employed Birch reduction (11), which is widely used to hydrogenate sp 2 carbon-based materials; in the case of C 60 and C 70 , Birch reduction yields C 60 H 36 and C 70 H 30 , respectively (12, 13). We find that up to 5 wt % of hydrogen can be incorporated in few-layer graphenes by Birch reduction. The sp 3 C-H bonds formed by the reduction of fewlayer graphenes are broken on heating or on irradiation with ultraviolet or laser radiation releasing all the hydrogen. Such chemical storage of a substantial amount of hydrogen in graphene is indeed noteworthy. We have carried out first-principles calculations to understand the nature of hydrogen in reduced graphene.
Results and DiscussionFew-layer graphene samples were prepared by the exfoliation of graphite oxide (EG) (9) and the arc evaporation of graphite under hydrogen (HG) (10). Atomic force microscopy (AFM) indicated that the average number of layers in EG and HG were 6-7 and 2-3, respectively (see Fig. S1). The Brunauer-EmmettTeller surface areas of EG and HG were 670 and 210 m 2 ∕g, respectively. We carried out Birch reduction of EG and HG with lithium in liquid ammonia (11)(12)(13). Elemental analysis of reduced EG (EGH) and HG (HGH) samples showed the hydrogen content to be around 5 wt % in the sample...