Heat treatment constitutes a key
synthesis step for nitrogen-doped
carbons, which have been investigated for applications to numerous
electro- and thermo-catalytic reactions. However, the conventional
approach relying on bulk heating limits our ability to tailor catalyst
properties due to the fast gasification of carbon-based materials
in reactive atmospheres such as NH3. In this paper, we
report the advantages of utilizing microwave technology for improving
the catalytic performance of nitrogen-doped carbon via selective and
rapid heating. We synthesized two distinct sets of nitrogen-doped
carbons from graphene oxide: one exhibiting micropores approximately
1 nm in width (HS) and another characterized by their
scarcity of micropores (NS). Despite their comparable
nitrogen contents, HS exhibits significantly higher activity
than NS in the electrochemical oxygen reduction reaction
(ORR) in an acidic electrolyte. These samples underwent further heat
treatment in NH3 or N2 using a conventional
tubular furnace or a single-mode microwave reactor apparatus. Our
results demonstrate that microwave heating limits the gasification
of carbon-based materials, which effectively permits heating up to
an average temperature of 1400 °C in NH3. Microwave
heating of HS in NH3 enhances its pore hydrophobicity
while maintaining the microporosity, substantially improving the ORR
activity. Conversely, microwave heating of HS in N2 considerably diminishes its ORR activity, despite enhancing
pore hydrophobicity and maintaining an adequate nitrogen species presence.
These findings emphasize the crucial role played by the coexistence
of carbon defects and specific nitrogen sites generated through heating
in a NH3 atmosphere within hydrophobic micropores for high
ORR activity. In summary, our data highlight the distinct advantages
of the high-temperature treatment of nitrogen-doped carbons in NH3 using microwave heating. This approach enables us to adjust
the reactive microenvironments, thereby improving catalytic performance
without sacrificing crucial active sites within micropores for ORR
catalysis.