Self-Organized 3D Porous Graphene Dual-Doped with Biomass-Sponsored Nitrogen and Sulfur for Oxygen Reduction and Evolution.

3D graphene-based materials offer immense potentials to overcome the challenges related to the functionality, performance, cost, and stability of fuel cell electrocatalysts. Herein, a nitrogen (N) and sulfur (S) dual-doped 3D porous graphene catalyst is synthesized via a single-row pyrolysis using biomass as solitary source for both N and S, and structure directing agent. The thermochemical reaction of biomass functional groups with graphene oxide facilitates in situ generation of reactive N and S species, stimulating the graphene layers to reorganize into a trimodal 3D porous assembly. The resultant catalyst exhibits high ORR and OER performance superior to similar materials obtained through toxic chemicals and multistep routes. Its stability and tolerance to CO and methanol oxidation molecules are far superior to commercial Pt/C. The dynamics governing the structural transformation and the enhanced catalytic activity in both alkaline and acidic media are discussed. This work offers a unique approach for rapid synthesis of a dual-heteroatom doped 3D porous-graphene-architecture for wider applications.