Improvement of Oxygen Reduction Performance in Alkaline Media by Tuning Phase Structure of Pd–Bi Nanocatalysts

Tuning the crystal phase of bimetallic nanocrystals offers an alternative avenue to improving their electrocatalytic performance. Herein, we present a facile and one-pot synthesis approach that is used to enhance the catalytic activity and stability toward oxygen reduction reaction (ORR) in alkaline media via control of the crystal structure of Pd-Bi nanocrystals. By merely altering the types of Pd precursors under the same conditions, the monoclinic structured Pd₅Bi₂ and conventional face-centered cubic (fcc) structured Pd₃Bi nanocrystals with comparable size and morphology can be precisely synthesized, respectively. Interestingly, the carbon-supported monoclinic Pd₅Bi₂ nanocrystals exhibit superior ORR activity in alkaline media, delivering a mass activity (MA) as high as 2.05 A/mg_Pd. After 10,000 cycles of ORR durability test, the monoclinic structured Pd₅Bi₂/C nanocatalysts still remain a MA of 1.52 A/mg_Pd, which is 3.6 times, 16.9 times, and 21.7 times as high as those of the fcc Pd₃Bi/C counterpart, commercial Pd/C, and Pt/C electrocatalysts, respectively. Moreover, structural characterizations of the monoclinic Pd₅Bi₂/C nanocrystals after the durability test demonstrate the excellent retention of the original size, morphology, composition, and crystal phase, greatly alleviating the leaching of the Bi component. This work provides new insight for the synthesis of multimetallic catalysts with a metastable phase and demonstrates phase-dependent catalytic performance.