Rh-doped PdAg nanoparticles as efficient methanol tolerance electrocatalytic materials for oxygen reduction

Direct methanol fuel cells (DMFCs) have received extensive attention on their high efficiency, high reliability, and no carbon emission. Unfortunately, the poor methanol tolerance and sluggish oxygen reduction reaction (ORR) at cathode have seriously hindered their further development. Herein we report the synthesis of a new class of Rh-doped PdAg alloy nanoparticles (NPs) for boosting ORR activity with high methanol tolerance capacity concurrently. The ORR mass activity of typical Rh₄Pd₄₀Ag₅₆ NPs is 4.2 times higher than that of commercial Pt catalyst. Moreover, it shows a great methanol tolerance capability by maintaining 92.4% in ORR mass activity in alkaline solution with 0.1 mol L^-1 methanol, against a big decrease of almost 100% for commercial Pt. Even after 30,000 potential cycles with 1.0 mol L^-1 methanol, Rh₄Pd₄₀Ag₅₆ NPs still retain ORR mass activity of up to 68.3%. DFT calculations reveal that excellent ORR performance with excellent methanol tolerance originates the active d-band-pinning engineering for an efficient site-independent electron-transfer. A generalized d-band mediated fine electron-transfer tuning path has blueprinted for effectively minimizing intrinsic ORR barriers with high current density. The present work highlights the key role of Rh doping in enhancing the ORR activity and methanol tolerance ability of PdAg NPs for future high-performance DMFCs.