Pr tuning the electronic structure of Pt cluster-on-(Ni-PrF₃) nanoparticle supported on carbon for highly efficient electrocatalytic hydrogen evolution and methanol oxidation reactions

Fuel cells are a highly promising class of energy conversion devices, with the potential to address the growing global demand for sustainable power. In this work, a Pt/Ni-PrF₃/C electrocatalyst was synthesized by incorporating PrF₃-doped nickel particles, which notably enhanced catalytic performance for both the hydrogen evolution reaction (HER) and methanol oxidation reaction (MOR). In 1.0 mol L^-1 KOH, the catalyst exhibited a low overpotential of 77.7 mV at 100 mA cm^-2 for the HER, and achieves an overpotential of 68.7 mV in simulated seawater (1.0 mol L^-1 KOH + 0.5 mol L^-1 NaCl). Meanwhile, in 1.0 mol L^-1 KOH + 1.0 mol L^-1 CH₃OH, it achieves a high mass activity of 4.58 A mg_Pt^-1 toward MOR. The combination of experimental characterization and density functional theory (DFT) calculations reveal that the introduction of Pr promotes charge transfer and optimizes the adsorption free energy of *H intermediate, yielding a value closest to zero, which indicates optimal adsorption strength. This synergistic modulation not only enhanced HER activity by facilitating the Tafel step via a downshift in the d-band center of Pt, but also improved MOR performance. Specifically, the enhanced selectivity toward the CHOOH pathway effectively suppresses *CO accumulation, mitigates CO poisoning, and contributes to the improved activity and stability observed during the MOR. Overall, this study proposes a rare-earth-mediated strategy using Pr-doped Ni to modulate the electronic structure of Pt, offering an effective route for designing advanced electrocatalysts for energy conversion applications.