Promoting H2O2 production via 2-electron oxygen reduction by coordinating partially oxidized Pd with defect carbon

Electrochemical synthesis of H2O2 through a selective two-electron (2e(-)) oxygen reduction reaction (ORR) is an attractive alternative to the industrial anthraquinone oxidation method, as it allows decentralized H2O2 production. Herein, we report that the synergistic interaction between partially oxidized palladium (Pd delta+) and oxygen-functionalized carbon can promote 2e(-) ORR in acidic electrolytes. An electrocatalyst synthesized by solution deposition of amorphous Pd delta+ clusters (Pd-3(delta+) and Pd-4(delta+)) onto mildly oxidized carbon nanotubes (Pd delta+-OCNT) shows nearly 100% selectivity toward H2O2 and a positive shift of ORR onset potential by 320mV compared with the OCNT substrate. A high mass activity (1.946Amg(-1) at 0.45V) of Pd delta+-OCNT is achieved. Extended X-ray absorption fine structure characterization and density functional theory calculations suggest that the interaction between Pd clusters and the nearby oxygen-containing functional groups is key for the high selectivity and activity for 2e(-) ORR.