Ga-Doped Pt-Ni Octahedral Nanoparticles as a Highly Active and Durable Electrocatalyst for Oxygen Reduction Reaction.

Bimetallic PtNi nanoparticles have been considered as a promising electrocatalyst for oxygen reduction reaction (ORR) in polymer electrolyte membrane fuel cells (PEMFCs) owing to their high catalytic activity. However, under typical fuel cell operating conditions, Ni atoms easily dissolve into the electrolyte, resulting in degradation of the catalyst and the membrane-electrode assembly (MEA). Here, we report gallium-doped PtNi octahedral nanoparticles on a carbon support (Ga-PtNi/C). The Ga-PtNi/C shows high ORR activity, marking an 11.7-fold improvement in the mass activity (1.24 A mgPt-1) and a 17.3-fold improvement in the specific activity (2.53 mA cm-2) compared to the commercial Pt/C (0.106 A mgPt-1 and 0.146 mA cm-2). Density functional theory calculations demonstrate that addition of Ga to octahedral PtNi can cause an increase in the oxygen intermediate binding energy, leading to the enhanced catalytic activity toward ORR. In a voltage-cycling test, the Ga-PtNi/C exhibits superior stability to PtNi/C and the commercial Pt/C, maintaining the initial Ni concentration and octahedral shape of the nanoparticles. Single cell using the Ga-PtNi/C exhibits higher initial performance and durability than those using the PtNi/C and the commercial Pt/C. The majority of the Ga-PtNi nanoparticles well maintain the octahedral shape without agglomeration after the single cell durability test (30,000 cycles). This work demonstrates that the octahedral Ga-PtNi/C can be utilized as a highly active and durable ORR catalyst in practical fuel cell applications.

Heterogeneous Structure of Ni-Mo Nanoalloys Decorated on MoOx for an Efficient Hydrogen Evolution Reaction Using Hydrogen Spillover.

Herein, a heterogeneous structure of Ni-Mo catalyst comprising Ni4Mo nanoalloys decorated on a MoOx matrix via electrodeposition is introduced. This catalyst exhibits remarkable hydrogen evolution reaction (HER) activity across a range of pH conditions. The heterogeneous Ni-Mo catalyst showed low overpotentials only of 24 and 86, 21 and 60, and 37 and 168 mV to produce a current density of 10 and 100 mA cm-2 (η10 and η100) in alkaline, acidic, and neutral media, respectively, which represents one of the most active catalysts for the HER. The enhanced activity is attributed to the hydrogen spillover effect, where hydrogen atoms migrate between the Ni4Mo alloys and the MoOx matrix, forming hydrogen molybdenum bronze as additional active sites. Additionally, the Ni4Mo facilitated the water dissociation process, which helps the Volmer step in the alkaline/neutral HER. Through electrochemical analysis, in situ Raman spectroscopy, and density functional theory calculations, the fast HER mechanism is elucidated.