Palladium deposits spontaneously grown on nickel foam for electro-catalyzing methanol oxidation: Effect of precursors

• Two nanosized Pd deposits were spontaneously grown on Ni foam via galvanic replacement.
• Different palladic precursors produced discrepant arrangements and coverages of Pd.
• Pd-4-Ni had more exposure of Ni atoms adjoined to Pd atoms on the catalytic interface.
• Higher catalytic activity of Pd-4-Ni toward MOR than Pd-2-Ni and Pd/C.

Methanol, a high-energy substance, is widely used for green fuel cells. However, the sluggish electrochemical methanol oxidation reaction (MOR) on state-of-the-art catalysts still requires for exploring high-performance and low-cost materials to further promote the reaction kinetics at low overpotentials. Here we carried out the first electrocatalytic comparison study of two Ni foam-supported Pd nanomaterials (Pd-2-Ni and Pd-4-Ni, respectively), obtained through the spontaneous galvanic replacement of Ni with different palladic precursors ([PdCl4]2- and [PdCl6]2−, respectively), toward MOR. With replacement, Pd deposits with discrepant arrangements and coverages were grown on the porous Ni support. Compared to commercial Pd/C, both Pd-2-Ni and Pd-4-Ni exhibited better mass activity and catalytic durability for MOR in alkaline media. More interestingly, different palladic precursors made a significant effect on the catalytic performance of the Ni foam-supported Pd deposits. In Pd-4-Ni, the 2:1 stoichiometric replacement of Ni with [PdCl6]2− enabled the incompact arrangement of Pd structures, with more exposure of Ni atoms adjoined to Pd atoms on the catalytic interface compared to Pd-2-Ni. As a result, with the favorable Ni-neighbor-Pd regime and the higher utilization efficiency of Pd atoms, the synthesized Pd-4-Ni catalyst provided a mass activity of approximately 1.5 times higher than Pd-2-Ni toward MOR.

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