Balancing Mass Transfer and Active Sites to Improve Electrocatalytic Oxygen Reduction by B,N Codoped C Nanoreactors

Mass transfer is critical in catalytic processes, especially when the reactions are facilitated by nanostructured catalysts. Strong efforts have been devoted to improving the efficacy and quantity of active sites, but often, mass transfer has not been well studied. Herein, we demonstrate the importance of mass transfer in the electrocatalytic oxygen reduction reaction (ORR) by tailoring the pore sizes. Using a confined-etching strategy, we fabricate boron- and nitrogen-doped carbon (B,N@C) electrocatalysts featuring abundant active sites but different porous structures. The ORR performance of these catalysts is found to correlate with diffusion of the reactant. The optimized B,N@C with trimodal-porous structures feature enhanced O₂ diffusion and better activity per heteroatomic site toward the ORR process. This work demonstrates the significance of the nanoarchitecture engineering of catalysts and sheds light on how to optimize structures featuring abundant active sites and enhanced mass transfer.