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Herein, we synthesized P- and N-doped carbon materials (PN-doped carbon materials) through controlled phosphoric acid treatment (CPAT) of folic acid (FA) and probed their ability to catalyze the oxygen reduction reaction (ORR) at the cathode of a fuel cell. Precursors obtained by heating FA in the presence of phosphoric acid at temperatures of 400-1000 °C were further annealed at 1000 °C to afford PN-doped carbon materials. The extent of precursor P doping was maximized at 700 °C, and the use of higher temperatures resulted in activation and increased porosity rather than in increased P content. The P/C atomic ratios of PN-doped carbon materials correlated well with those of the precursors, which indicated that CPAT is well suited for the preparation of PN-doped carbon materials. The carbon material prepared using a CPAT temperature of 700 °C exhibited the highest ORR activity and was shown to contain -C-PO 2 and -C-PO 3 moieties as the major P species and pyridinic N as the major N species. Moreover, no N-P bonds were detected. It was concluded that the presence of -C-PO 2 and -C-PO 3 units decreases the work function and thus raises the Fermi level above the standard O 2 /H 2 O reduction potential, which resulted in enhanced ORR activity. Finally, CPAT was concluded to be applicable to the synthesis of PN-doped carbon materials from N-containing organic compounds other than FA.

Synthesis of P- and N-doped carbon catalysts for the oxygen reduction reaction via controlled phosphoric acid treatment of folic acid