Dipole-Dipole Tuned Electronic Reconfiguration of Defective Carbon Sites for Efficient Oxygen Reduction into H2O2.

Abstract

Metal-free carbon-based materials are one of the most promising electrocatalysts toward 2-electron oxygen reduction reaction (2e-ORR) for on-site production of hydrogen peroxide (H2O2), which however suffer from uncontrollable carbonizations and inferior 2e-ORR selectivity. To this end, a polydopamine (PDA)-modified carbon catalyst with a dipole-dipole enhancement is developed via a calcination-free method. The H2O2 yield rate outstandingly reaches 1.8mol gcat -1 h-1 with high faradaic efficiency of above 95% under a wide potential range of 0.4-0.7 VRHE, overwhelming most of carbon electrocatalysts. Meanwhile, within a lab-made flow cell, the synthesized ORR electrode features an exceptional stability for over 250h, achieved a pure H2O2 production efficacy of 306g kWh-1. By virtue of its industrial-level capabilities, the established flow cell manages to perform a rapid pulp bleaching within 30min. The superior performance and enhanced selectivity of 2e-ORR is experimentally revealed and attributed to the electronic reconfiguration on defective carbon sites induced by non-covalent dipole-dipole influence between PDA and carbon, thereby prohibiting the cleavage of O-O in OOH intermediates. This proposed strategy of dipole-dipole effects is universally applicable over 1D carbon nanotubes and 2D graphene, providing a practical route to design 2e-ORR catalysts.