Pyrolytic transition metal nitrogen-carbon (M-N/C) materials are considered as the most promising alternatives for platinum-based catalysts toward oxygen reduction reaction (ORR). As the proton-coupled electron transfer step in ORR has been proven to be a rate-determining step in the M-N/C catalysts, we envisaged that building a protophilic surface might be helpful to enhance the ORR activity. Herein, a polyaniline decoration strategy was put forward and realized to confer the Fe-N/C catalyst with a surface protophilic environment. A 20 mV positive shift in half-wave potential was observed owing to the enriched interfacial proton concentration, corresponding to a tripled turnover frequency under acidic conditions (from 0.46 to 1.28 e·s-1·sites-1). Our work blazed a new path toward the design of M-N/C ORR catalysts, commencing via the ORR kinetics.
Keywords: Fe−N/C catalyst; ORR; PANI; PCET; Surface protophilic environment.