Plasmon assisted generation of solvated electrons from low work function scandium oxide and their utilization for enhanced nitrogen reduction

Solvated or hydrated electrons represent smallest possible anion, which can exist. Due to enormous redox activity these electrons, entrapped in solvent cage, have enormous potential in the field of chemical transformation. However, wide utilization of hydrated electrons is significantly restricted by the methods of their creation, which are either highly energy demanding or based on less probable two photons process. In this work, we propose a rationally designed plasmon active nanostructures coated with low work function material for efficient production and utilization of hydrated electrons. In such case, the coupled plasmon active nanostructure can efficiently convert photon energy in the energy of plasmon excited hot electrons. The electrons are subsequently injected in the low work function material (in this case scandium oxide), facilitating their transfer to surrounding electrolyte. Alternatively, the injected electrons can “wait” in the scandium oxide layer for additional plasmon triggering and injecting through two photons process. The creation of hydrated electrons was confirmed by various techniques, including fiber based optical spectroscopy and electronic paramagnetic spectroscopy. The redox potential of hydrated electrons was subsequently demonstrated in nitrogen reduction, where the 28.3 and 38.0 µmol·g -1 ·h -1 NH 3 yield were reached in photo- and photoelectrochemical regimes respectively. Comparison with alternative method and materials, used for NRR performing in “photo-mode” (not based on hydrated electrons utilization) indicate the huge potential of the proposed structure and approach. • A rationally designed plasmon-active nanostructures coated with LWF material is proposed. • The structure created is used for efficient production and utilization of hydrated electrons. • The hydrated electrons were subsequently used for nitrogen reduction. • An excellent ammonia yield was obtained in such a way.