Rapid Synthesis and Microenvironment Optimization of Hierarchical Porous Fe─N─C Catalysts for Enhanced ORR in Microbial Fuel Cells

Abstract Here, an approach to produce a hierarchical porous Fe‐N‐C@TABOH catalyst with densely accessible high intrinsic active FeN_x sites is proposed. The method involves a single‐step pyrolysis of Zn/Fe‐zeolitic imidazolate framework (Zn/Fe‐ZIF‐H) with tetrabutylammonium hydroxide (TABOH) micelles, which is obtained by utilizing TABOH as a structural template and electronic mediator at room temperature for a brief duration of 16 min. Notably, the yield of Zn/Fe‐ZIF‐H is 3.5 times that of Zn/Fe‐ZIF‐N prepared by conventional method. Results indicate that in addition to expediting synthesis and increasing yield of the Zn/Fe‐ZIF‐H, the TABOH induces a hierarchical porous structure and fosters the formation of more and higher intrinsic active FeN_x moieties in Fe_x‐N‐C@TABOH, showing that TABOH is a multifunctional template. Crucially, the increased mesoporosity/external surface area and optimized microenvironment of Fe‐N‐C@TABOH significantly enhance ORR activity by facilitating the formation of high intrinsic active FeN_x sites, increasing accessible FeN_x sites, and reducing mass transfer resistance. Through structure tailoring and microenvironment optimization, the resulting Fe‐N‐C@TABOH exhibits superior ORR performance. DFT calculation further validates that the synergistic effect of these two factors leads to low ORR barrier and optimized ^*OH adsorption energy. This study underscores the importance of structure and electronic engineering in the development of highly active ORR catalysts.