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Galvanic Replacement-Mediated Synthesis of Ni-Supported Pd Nanoparticles with Strong Metal-Support Interaction for Methanol Electro-oxidation.

Herein, well-defined Pd nanoparticles (NPs) developed on Ni substrate (Pd NPs/Ni) are synthesized via a facile galvanic replacement reaction (GRR) route performed in ethaline-based deep eutectic solvent (DES). For comparison, a Pd NPs/Ni composite is also prepared by the GRR method conducted in an aqueous solution. The Pd NPs/Ni obtained from the ethaline-DES is catalytically more active and durable for the methanol electro-oxidation reaction (MOR) than those of the counterpart derived from conventional aqueous solution and commercial Pd/C under alkaline media. Detailed kinetic analysis indicates that the unique solvent environment offered by ethaline plays vital roles in adjusting the reactivity of the active species and their mass transport properties to control over the genesis of the Pd NPs/Ni nanocomposite. The resulting Pd NPs/Ni catalyst possesses a homogeneous dispersion of Pd NPs with a strong Pd (metal)-Ni (support) interaction. This structure enhances the charge transfer between the support and the active phases, and optimizes the adsorption energy of OH- and CO on the surface, leading to superior electrocatalytic performance. This work provides a novel GRR strategy performed in ethaline-DES to the rational design and construction of advanced metal/support catalysts with strong interaction for improving the activity and durability for MOR.