Boosting Oxygen Reduction Reaction Selectivity in Metal Nanoparticles with Polyoxometalates

The lack of selectivity toward the oxygen reduction reaction (ORR) in metal nanoparticles can be linked to the generation of intermediates. This constitutes a crucial constraint on the performance of specific electrochemical devices, such as fuel cells and metal–air batteries. To boost selectivity of metal nanoparticles, a novel methodology that harnesses the unique electrocatalytic properties of polyoxometalates (POM) to scavenge undesired intermediates of the ORR (such as HO 2 − ) promoting selectivity is proposed. It involves the covalent functionalization of metal nanoparticle's surface with an electrochemically active capping layer containing a new sulfur‐functionalized vanadium‐based POM (AuNP@POM). To demonstrate this approach, preformed thiolate Au(111) nanoparticles with a relatively poor ORR selectivity are chosen. The dispersion of AuNP@POM on the surface of carbon nanofibers (CNF) enhances oxygen diffusion, and therefore the ORR activity. The resulting electrocatalyst (AuNP@POM/CNF) exhibits superior stability against impurities like methanol and a higher pH tolerance range compared to the standard commercial Pt/C. The work demonstrates for the first time, the use of a POM‐based electrochemically active capping layer to switch on the selectivity of poorly selective gold nanoparticles, offering a promising avenue for the preparation of electrocatalyst materials with improved selectivity, performance, and stability for ORR‐based devices.