This study demonstrates the direct utilization of plasmon hot electrons in the hydrogen evolution reaction (HER) using visible light. A plasmonic nanohybrid system, NiO/Au/[Co(1,10-Phenanthrolin-5-amine)2(H2O)2], was assembled to minimize thermal contributions and maximize hot carrier effects. Combining photoelectrocatalysis with in situ spectroscopies revealed a reaction mechanism where plasmon-induced hot electrons are transferred to phenanthroline ligands, facilitating proton-electron transfer steps for hydrogen generation. The catalytic response to light modulation supports a hot carrier-mediated process with a minor positive heat contribution.

Ananta Dey, Amal Mendalz, Anna Wach, Robert Bericat Vadell, Vitor R. Silveira, Paul Maurice Leidinger, Thomas Huthwelker, Vitalii Shtender, Zbynek Novotny, Luca Artiglia, Jacinto Sá