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Graphene, being one-atom thick, is extremely sensitive to the presence ofadsorbed atoms and molecules and, more generally, to defects such as vacancies,holes and/or substitutional dopants. This property, apart from being directlyusable in molecular sensor devices, can also be employed to tune grapheneelectronic properties. Here we briefly review the basic features ofatomic-scale defects that can be useful for material design. After a briefintroduction on isolated $p_z$ defects, we analyse the electronic structure ofmultiple defective graphene substrates, and show how to predict the presence ofmicroscopically ordered magnetic structures. Subsequently, we analyse the morecomplicated situation where the electronic structure, as modified by thepresence of some defects, affects chemical reactivity of the substrate towardsadsorption (chemisorption) of atomic/molecular species, leading to preferentialsticking on specific lattice positions. Then, we consider the reverse problem,that is how to use defects to engineer graphene electronic properties. In thiscontext, we show that arranging defects to form honeycomb-shaped superlattices(what we may call "supergraphenes") a sizeable gap opens in the band structureand new Dirac cones are created right close to the gapped region. Similarly, weshow that substitutional dopants such as group IIIA/VA elements may have gappedquasi-conical structures corresponding to massive Dirac carriers. All thesepossible structures might find important technological applications in thedevelopment of graphene-based logic transistors.

The effect of atomic-scale defects and dopants on graphene electronic structure