Catalytic sub-surface etching of nanoscale channels in graphite

Catalytic hydrogenation of graphite has recently attracted renewed attention, as a route for nano-patterning of graphene and to produce graphene nano-ribbons. These reports show that metallic nanoparticles etch surface layers of graphite, or graphene anisotropically along the crystallographic zigzag <11-20> or armchair <1010> directions. On graphene the etching direction can be influenced by external magnetic fields or the substrate. Here we report the sub-surface etching of highly oriented pyrolytic graphite (HOPG) by Ni nanoparticles, to form a network of tunnels, as seen by SEM and STM. In this new nanoporous form of graphite, the top layers bend inward on top of the tunnels, while their local density of states remains fundamentally unchanged. Engineered nanoporous tunnel networks in graphite allow further chemical modification and may find applications in storage or sensing.