In situ electrochemical activation as a generic strategy for promoting the electrocatalytic hydrogen evolution reaction and alcohol electro-oxidation in alkaline medium.

In situ electrochemical activation as a new pre-treatment method is extremely effective for enhanced electrocatalytic performances for different applications. With the help of this method, in situ surface modification of electrocatalyst is achieved without using pre-made seeds or complex synthesis procedure. Herein, with the purpose of finding an in situ and simple electrochemical activation protocol, the green synthesis of Au/Pd nanoparticles (AuPd) by means of polyoxometalate (POM) is reported. Structural analysis of the AuPd nanohybrid unveil the Au-core/Pd-shell structure which surrounded by POM. We propose a novel cathodic electrochemical activation in phosphate buffer solution which can greatly boost the electrocatalytic activity of the as-prepared AuPd and Pd electrocatalyst not only for hydrogen evolution reaction (HER) as a model of electro-reduction, but also for methanol and ethanol electro-oxidation reaction (MOR & EOR). For the HER in 1 M NaOH solution, after the electrochemical activation, the needed potential to drive a geometrical current density of 10 mA cm -2 significantly decreases from - 400 mV vs. the reversible hydrogen electrode (RHE) to -290 mV vs. RHE. For the EOR and MOR, electrochemically activated AuPd realized 3.4- and 2.9- fold increase in mass current density (mA mg Pd -1 ) with respect to the pristine AuPd electrocatalyst, respectively.