Platinum nanoparticles embedded in pyrolyzed nitrogen-containing cobalt complexes for high methanol-tolerant oxygen reduction activity

High oxygen reduction activity of methanol-tolerant catalysts was successfully reported using platinum nanoparticles embedded in cobalt-based nitrogen-containing complexes supported on carbon blacks (Pt–N-complex/C). The oxygen reduction reaction (ORR) of the Pt–N-complex/C was attributed to four-electron transfer pathway in which oxygen was directly reduced to water, yielding four electrons. In a methanol-containing solution, the platinum intrinsically favors the methanol oxidation reaction over the ORR, which is a major drawback for direct methanol fuel cells (DMFCs). In comparison, when the Pt–N-complex/C is introduced in a methanol-containing solution, not only is the methanol oxidation suppressed but also the four-electron-transfer in the ORR is maintained up to the diffusion-limiting region. Physicochemical characterization of the Pt–N-complex/C indicates that pyrrolic N-type poly-aromatic hydrocarbons were formed in a network structure around the catalysts and prevented them from the methanol oxidation reaction. In a DMFC test at elevated methanol concentrations, the one with the Pt–N-complex/C cathode showed superior stability over the one with the Pt-based cathode, which may offer a solution to the methanol crossover problem in DMFCs.