Electrochemical dealloying as a tool to tune the porosity, composition and catalytic activity of nanomaterials

Electrochemical dealloying as a post-treatment can greatly improve the catalytic activity of nanoparticles. To date, selecting suitable conditions to reach desired porosity, composition and catalytic activity is based on trial-and-error-attempts, due to insufficient understanding of the electrochemically induced morphological and compositional changes of the nanoparticles. These changes are elucidated here by combining electrochemistry with identical location electron microscopy analyses and linking them to the electrocatalytic properties of the obtained nanocatalysts. Using AgAu alloy nanoparticles and the hydrogen evolution reaction as a model system, the influence of cyclic voltammetry parameters on the catalytic activity upon electrochemical dealloying is investigated. Increasing the number of cycles initially results in a decreased Ag content and a sharp improvement in activity. Additional dealloying increases the nanoparticle porosity, while marginally altering their composition, due to surface motion of atoms. Since this is accompanied by particle aggregation, a decrease in catalytic activity results upon extensive cycling. This transition between porosity formation and particle aggregation marks the optimum for nanocatalyst post-production. The gained insights may aid speeding up the development of new materials by electrochemical dealloying as an easy-to-control post-processing route to tune the properties of existing nanoparticles, instead of having to alter usually delicate synthesis routes as a whole. Electrochemical dealloying is presented as a versatile tool to fine-tune the properties and activity of electrocatalysts.