Deciphering the Role of Quaternary N in O₂ Reduction over Controlled N-Doped Carbon Catalysts

© 2020 American Chemical Society. Nitrogen-doped carbon catalysts prepared from amino-functionalized metal-organic frameworks [amino-MIL-101(Al)] were investigated for the oxygen-reduction reaction (ORR) with special emphasis on elucidating the role of different nitrogen species (e.g., pyridinic, pyrrolic, and quaternary N) as active catalytic sites. Careful optimization of pyrolysis temperature of the amino-MIL-101(Al) leveraged the synthesis of the catalysts with or without quaternary N functionalities. This allowed us to investigate the type(s) of N species responsible for the ORR catalysis and thus address the conflicting results reported so far regarding the pyridinic and/or quaternary N as active sites for ORR catalysis via four-electron transfer (4e-) pathways. Our findings suggest that the total nitrogen content in the catalysts does not influence the ORR, while…