Controlled Dealloying of Alloy Nanoparticles toward Optimization of Electrocatalysis on Spongy Metallic Nanoframes

Atomic-level understanding of the structural transformations of multimetallic nanoparticles triggered by external stimuli is of vital importance to the enhancement of our capabilities to fine-tailor the key structural parameters and thereby to precisely tune the properties of the nanoparticles. Here, we show that, upon thermal annealing in a reducing atmosphere, Au@Cu₂O core-shell nanoparticles transform into Au-Cu alloy nanoparticles with tunable compositional stoichiometries that are predetermined by the relative core and shell dimensions of their parental core-shell nanoparticle precursors. The Au-Cu alloy nanoparticles exhibit distinct dealloying behaviors that are dependent upon their Cu/Au stoichiometric ratios. For Au-Cu alloy nanoparticles with Cu atomic fractions above the parting limit, nanoporosity-evolving percolation dealloying occurs upon exposure of the alloy nanoparticles to appropriate chemical etchants, resulting in the formation of particulate spongy nanoframes with solid/void bicontinuous morphology composed of hierarchically interconnected nanoligaments. The nanoporosity evolution during percolation dealloying is synergistically guided by two intertwining structural rearrangement processes, ligament domain coarsening driven by thermodynamics and framework expansion driven by Kirkendall effects, both of which can be maneuvered by controlling the Cu leaching rates during the percolation dealloying. The dealloyed nanoframes possess large open surface areas accessible by the reactant molecules and high abundance of catalytically active undercoordinated atoms on the ligament surfaces, two unique structural features highly desirable for high-performance electrocatalysis. Using the room temperature electro-oxidation of methanol as a model reaction, we further demonstrate that, through controlled percolation dealloying of Au-Cu alloy nanoparticles, both the electrochemically active surface areas and the specific activity of the dealloyed metallic nanoframes can be systematically tuned to achieve the optimal electrocatalytic activities.