In this study, we present microporous carbon (MPC), hollow microporous carbon (HMC) and hierarchically porous carbon (HPC) to demonstrate the importance of strategical designing of nanoarchitectures in achieving advanced catalyst (or electrode) materials, especially in the context of oxygen reduction reaction (ORR). Based on the electrochemical impedance spectroscopy and ORR studies, we identify a marked structural effect depending on the porosity. Specifically, mesopores are found to have the most profound influence by significantly improving electrochemical wettability and accessibility. We also identify that macropore contributes to the rate capability of the porous carbons. The results of the rotating ring disk electrode (RRDE) method also demonstrate the advantages of strategically designed double-shelled nanoarchitecture of HPC to increase the overall electron transfer number (n) closer to four by offering a higher chance of the double two-electron pathways. Next, selective doping of highly active Fe-N x sites on HPC is obtained by increasing the nitrogen content in HPC. As a result, the optimized Fe and N co-doped HPC demonstrate high ORR catalytic activity comparable to the commercial 20 wt% Pt/C in alkaline electrolyte. Our findings, therefore, strongly advocate the importance of a strategic design of advanced catalyst (or electrode) materials, especially in light of both structural and doping effects, from the perspective of nanoarchitectonics.
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