LAUSR

Abstract To enhance the catalytic efficiency of graphene quantum dot (GQD) for ORR, the role of S-dopant and S-linker is explored here by utilizing the first-principles density functional theory-based approach. The ORR efficiency is found to be changed on different active sites with the variation of dopant position and dopant configuration on the sulfurized GQD. Charge transfer from the dopant site to the active sites and to the intermediates, as well as the binding energy of intermediates on the active sites play an important role to realize the potential determining step, onset potential and the overpotential for ORR. The increase in the doping concentration of S or the presence of oxygen is found to drastically enhance the ORR efficiency of GQD. Furthermore, S-linkers are exploited to connect two GQDs entangled or twisted with each other and resulting in a rather complex system. The combined effect of entangling, S-linkers and presence of a single N dopant at the meta position of the active site resulted in the adsorption of the intermediates with optimum binding strength. Consequently, the ORR activity is found to be enhanced, thereby resulting in a metal-free and cost-effective electrocatalyst with efficiency similar to the Pt-based metal catalysts.