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Engineering Three-Dimensional (3D) Out-of-Plane Graphene Edge Sites for Highly-Selective Two-Electron Oxygen Reduction Electrocatalysis

Selective two-electron oxygen reduction reaction (ORR) offers a promising route for hydrogen peroxide synthesis, and defective sp2 carbon-based materials are attractive, low-cost electrocatalysts for this process. However, due to a wide range of possible defect structures formed during material synthesis, identification and fabrication of precise active sites remain a challenge. Here, we report a graphene edgebased electrocatalyst for two-electron ORR - nanowire-templated three-dimensional fuzzy graphene (NT3DFG). NT-3DFG exhibits excellent efficiency (onset potential of 0.79 $\pm$ 0.01 V versus RHE), selectivity (93 $\pm$ 3 % H2O2), and tunable ORR activity as a function of graphene edge site density. Using spectroscopic surface characterization and density functional theory calculations, we find that NT-3DFG edge sites are readily functionalized by carbonyl (C=O) and hydroxyl (C-OH) groups under alkaline ORR conditions. Our calculations indicate that multiple site configurations at both armchair and zigzag edges may achieve a local coordination environment that allows selective, two-electron ORR. We derive a general geometric descriptor based on the local coordination environment that provides activity predictions of graphene surface sites within ~0.1 V of computed values. Herein we combine synthesis, spectroscopy, and simulations to improve active site characterization and accelerate carbon-based electrocatalyst discovery.