Urea synthesis by Plasmon-Assisted N2 and CO2 co-electrolysis onto heterojunctions decorated with silver nanoparticles

• One-pot mechanochemical synthesis of AgNPs over metallic heterojunction . • N 2 and CO 2 co-electrolysis under light irradiation . • Electrocatalysis improved by Localized Surface Plasmon Resonance (LSPR) of AgNPs. • Electrochemical C-N coupling assisted by LSPR with major contribution of AgNPs. • Increase of Faradaic Efficiency and urea yield at lower overpotentials in LSPR conditions. The N 2 + CO 2 co-electrolysis to urea synthesis has become a promising alternative to the energy intensive traditional processes for urea production. However, there are still challenges in this approach, especially due to the competition with HER (Hydrogen Evolution Reaction) leading to low efficiency. Electrochemistry assisted by localized surface plasmon resonance (LSPR) using metal nanoparticles has been reported to enhance different electrochemical reactions. Here we report an electrochemical LSPR assisted urea synthesis using Ag nanoparticles (NPs) supported on BiVO 4 /BiFeO 3 catalyst mechanochemically synthesized. The electrochemical experiments were performed under dark and upon plasmon excitation at the LSPR region of Ag NPs. Our results demonstrated that exciting in the LSPR range, urea yield rate and Faradic efficiency were considerably improved with reduced overpotential, 19.2 μmol h −1 g −1 and FE 24.4% at +0.1 V vs RHE compared to 9.6 μmol h −1 g −1 and FE 9.4% at −0.2 V vs RHE under dark conditions. Further in situ FTIR-RAS experiments for mechanism investigation revealed the presence of N-H and C-N intermediates and the real effect of Ag plasmon excitation on HER and N 2 + CO 2 co-electrolysis. Theoretical calculations confirm the energy of the species involved in C-N coupling as well the role of the complex catalytic sites, which agrees with XAS measurements.