4.6 Article

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

Journal

ACS SUSTAINABLE CHEMISTRY & ENGINEERING
Volume 11, Issue 14, Pages 5345-5355

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acssuschemeng.2c05220

Keywords

bimetallic alloy; bifunctional; oxygen reduction; temperature-dependent methanol oxidation; 3D Bode plot; alkaline direct methanol fuel cells

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A sphere-like PdNi alloy (sPdNiA) was developed to enhance the electrocatalytic activity of the catalysts for the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) in 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 (E1/2) of similar to 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 mgPd-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 degrees C) with a lower activation energy (Ea). For the first time, the direct methanol fuel cell is fabricated utilizing sPdNiA as a bifunctional electrode, exhibited a higher peak power density (Pmax) 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.

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