N,P-coordinated fullerene-like carbon nanostructures with dual active centers toward highly-efficient multi-functional electrocatalysis for CO2RR, ORR and Zn-air battery

Abstract

Modulating the charge distribution over the carbon skeleton via heteroatom doping is critical for creating active centres for efficient metal-free electrocatalysts. However, effective approaches to precisely control heteroatom co-doping to guide catalytic activities are still lacking. Herein, a P and N-coordinated fullerene-like carbon (N,P-FC) multi-functional catalyst was constructed via a facile soft-template pyrolysis method, which achieves impressive activity for the electrochemical reduction of CO₂ to CO (CO₂RR, 83.3% faradaic efficiency for CO (FE_CO), a high current density of ∼24 mA cm⁻² at −0.8 V), along with high selectivity and long-term stability. The activity of N,P-FC for CO₂RR is strongly dependent on the P/N atomic ratio. Also, N,P-FC possesses an impressive oxygen reduction reaction (ORR) performance with a half-wave overpotential (E_1/2) of 0.910 V, 79 mV higher than that of commercial Pt/C, and it outperforms all documented carbon-based electrocatalysts. Combined theoretical calculation studies suggest that the P-coordinated C site is more active for CO₂RR, while the N-coordinated neighboring C site is responsible for ORR in this catalyst. This work highlights a new concept for modulating surface charge redistribution by heteroatom co-doping and morphology control toward designing efficient and low-cost electrocatalysts.