Nitrogen-doped graphene as a metal-free catalyst for oxygen reduction was synthesized by heat-treatment of graphene using ammonia. It was found that the optimum temperature was 900 °C. The resulting catalyst had a very high oxygen reduction reaction (ORR) activity through a four-electron transfer process in oxygen-saturated 0.1 M KOH. Most importantly, the electrocatalytic activity and durability of this material are comparable or better than the commercial Pt/C (loading: 4.85 µg_Pt cm⁻²). XPS characterization of these catalysts was tested to identify the active N species for ORR.

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.