Two-step boron and nitrogen doping in graphene for enhanced synergistic catalysis.

Two-dimensional materials, such as graphene and monolayer hexagonal BN (h-BN), are attractive for demonstrating fundamental physics in materials and potential applications in next-generation electronics. Atomic sheets containing hybridized bonds involving elements B, N and C over wide compositional ranges could result in new materials with properties complementary to those of graphene and h-BN, enabling a rich variety of electronic structures, properties and applications. Here we report the synthesis and characterization of large-area atomic layers of h-BNC material, consisting of hybridized, randomly distributed domains of h-BN and C phases with compositions ranging from pure BN to pure graphene. Our studies reveal that their structural features and bandgap are distinct from those of graphene, doped graphene and h-BN. This new form of hybrid h-BNC material enables the development of bandgap-engineered applications in electronics and optics and properties that are distinct from those of graphene and h-BN.

Tailoring the electronic arrangement of graphene by doping is a practical strategy for producing significantly improved materials for the oxygen-reduction reaction (ORR) in fuel cells (FCs). Recent studies have proven that the carbon materials doped with the elements, which have the larger (N) or smaller (P, B) electronegative atoms than carbon such as N-doped carbon nanotubes (CNTs), P-doped graphite layers and B-doped CNTs, have also shown pronounced catalytic activity. Herein, we find that the graphenes doped with the elements, which have the similar electronegativity with carbon such as sulfur and selenium, can also exhibit better catalytic activity than the commercial Pt/C in alkaline media, indicating that these doped graphenes hold great potential for a substitute for Pt-based catalysts in FCs. The experimental results are believed to be significant because they not only give further insight into the ORR mechanism of these metal-free doped carbon materials, but also open a way to fabricate other new low-cost NPMCs with high electrocatalytic activity by a simple, economical, and scalable approach for real FC applications. © 2011 American Chemical Society