Bidirectional Regulation of Nitrilase Reaction Specificity by Tuning the Characteristic Distances between Key Residues and Substrate

Development of highly active and durable catalysts for oxygen reduction reaction (ORR) alternative to Pt-based catalyst is an essential topic of interest in the research community but a challenging task. Here, we have developed a new type of face-centered tetragonal (fct) PdFe-alloy nanoparticle-encapsulated Pd (fct-PdFe@Pd) anchored onto nitrogen-doped graphene (NG). This core–shell fct-PdFe@Pd@NG hybrid is fabricated by a facile and cost-effective technique. The effect of temperature on the transformation of face-centered cubic (fcc) to fct structure and their effect on ORR activity are systematically investigated. The core–shell fct-PdFe@Pd@NG hybrid exerts high synergistic interaction between fct-PdFe@Pd NPs and NG shell, beneficial to enhance the catalytic ORR activity and excellent durability. Impressively, core–shell fct-PdFe@Pd@NG hybrid exhibits an excellent catalytic activity for ORR with an onset potential of ∼0.97 V and a half-wave potential of ∼0.83 V versus relative hydrogen electrode, ultrahigh current density, and decent durability after 10 000 potential cycles, which is significantly higher than that of marketable Pt/C catalyst. Furthermore, the core–shell fct-PdFe@Pd@NG hybrid also shows excellent tolerance to methanol, unlike the commercial Pt/C catalyst. Thus, these findings open a new protocol for fabricating another core–shell hybrid by facile and cost-effective techniques, emphasizing great prospect in next-generation energy conversion and storage applications.