Sphere-like PdNi Alloy: Unveiling the Twin Functional Properties toward Oxygen Reduction and Temperature-Dependent Methanol Oxidation for Alkaline Direct Methanol Fuel Cells

The development of high-performance bifunctional palladium-based (Pd) alloys for the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) is a great challenge in direct methanol fuel cells. The incorporation of an oxophilic atom into the Pd atom is an effective strategy to enhance the electrocatalytic activity of the catalysts. Herein a sphere-like PdNi alloy (sPdNiA) was developed via a simple hydrazine-assisted reduction method to overcome the kinetic drawbacks of palladium and delivers superior ORR/MOR performance. The successful alloy formation, the induced strain effect in the electronic structure, and structural characteristics of the sPdNiA were confirmed through XRD, XPS, and HR-TEM studies. As a result, for ORR, the sPdNiA exhibits a positive halfwave potential (E_1/2) of ∼0.854 V (vs RHE) compared to the pure Pd (0.833 V vs RHE) nanoparticles. For MOR, the sPdNiA presents the low onset potential and high mass activity of 518 mA mg_Pd^–1 in 1.0 M KOH electrolyte. Furthermore, the temperature-dependent MOR and 3D Bode plot investigations reveal a five-fold higher mass activity at elevated temperature (60 °C) with a lower activation energy (E_a). For the first time, the direct methanol fuel cell is fabricated utilizing sPdNiA as a bifunctional electrode, exhibited a higher peak power density (P_max) of 34 mW cm^–2, whereas 22 mW cm^–2 was obtained for Pd Np-based fuel cells. Incorporating oxophilic atom (Ni) not only improves the performance of Pd but significantly reduces the cost of the catalyst material by lowering the Pd content.