Exposing Fe–N–C catalysts to H2O2-byproduct leaves their catalytic sites untouched but decreases the turnover frequency via oxidation of the carbon surface.

Graphene has been highlighted recently as a promising material for energy conversion due to its unique properties deriving from a two-dimensional layered structure of sp 2 -hybridized carbon. Herein, N-doped graphene (NGr) is developed for its application in oxygen reduction reactions (ORRs) in acidic media, and additional doping of B or P into the NGr is attempted to enhance the ORR performance. The NGr exhibits an onset potential of 0.84 V and a mass activity of 0.45 mA mg À1 at 0.75 V. However, the B, N-(BNGr) and P, N-doped graphene (PNGr) show onset potentials of 0.86 and 0.87 V, and mass activities of 0.53 and 0.80 mA mg À1 , respectively, which are correspondingly 1.2 and 1.8 times higher than those of the NGr. Moreover, an additional doping of B or P effectively reduces the production of H 2 O 2 in the ORRs, and shows much higher stability than that of Pt/C in acidic media. It is proposed that the improvement in the ORR activity results from the enhanced asymmetry of the spin density or electron transfer on the basal plane of the graphene, and the decrease in the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the graphene through additional doping of B or P.

Catalysis is a key technology for the synthesis of renewable fuels through electrochemical reduction of CO2 . However, successful CO2 reduction still suffers from the lack of affordable catalyst design and understanding the factors governing catalysis. Herein, we demonstrate that the CO2 conversion selectivity on Sn (or SnOx /Sn) electrodes is correlated to the native oxygen content at the subsurface. Electrochemical analyses show that the reduced Sn electrode with abundant oxygen species effectively stabilizes a CO2 (.-) intermediate rather than the clean Sn surface, and consequently results in enhanced formate production in the CO2 reduction. Based on this design strategy, a hierarchical Sn dendrite electrode with high oxygen content, consisting of a multi-branched conifer-like structure with an enlarged surface area, was synthesized. The electrode exhibits a superior formate production rate (228.6 μmol h(-1)  cm(-2) ) at -1.36 VRHE without any considerable catalytic degradation over 18 h of operation.