Heterojunction‐Based Electron Donators to Stabilize and Activate Ultrafine Pt Nanoparticles for Efficient Hydrogen Atom Dissociation and Gas Evolution

Platinum (Pt) is the most effective bench‐marked catalyst for producing renewable and clean hydrogen energy by electrochemical water splitting. There is demand for high HER catalytic activity to achieve efficient utilization and minimize the loading of Pt in catalysts. In this work, we significantly boost the HER mass activity of Pt nanoparticles in Ptx/Co to 8.3 times higher than that of commercial Pt/C by using Co/NC heterojunctions as a heterogeneous version of electron donors. The highly coupled interfaces between Co/NC and Pt metal enrich the electron density of Pt nanoparticles to facilitate the adsorption of H+, the dissociation of Pt−H bonds and H2 release, giving the lowest HER overpotential of 6.9 mV vs. RHE at 10 mA cm−2 in acid among reported HER electrocatalysts. Given the easy scale‐up synthesis due to the stabilization of ultrafine Pt nanoparticles by Co/NC solid ligands, Ptx/Co can even be a promising substitute for commercial Pt/C for practical applications. Co/NC heterojunctions are used as “solid ligands” to control the growth of as‐supported ultrafine Pt nanoparticles via donating electrons. Ultrafine Pt nanoparticles with enhanced electron density promote the proton capture from electrolyte to catalyst surface, the dissociation of Pt−H bonds and successive release of H2 molecules from the Pt surface.