Plasmon-Assisted Ammonia Electrosynthesis.

Ammonia is a promising liquid-phase carrier for the storage, transport, and deployment of carbon-free energy. However, the realization of an ammonia economy is predicated on the availability of green methods for the production of ammonia powered by electricity from renewable sources or by solar energy. Here, we demonstrate the synthesis of ammonium from nitrate powered by a synergistic combination of electricity and light. We use an electrocatalyst composed of gold nanoparticles, which have dual attributes of electrochemical nitrate reduction activity and visible-light-harvesting ability due to their localized surface plasmon resonances. Plasmonic excitation of the electrocatalyst induces ammonium synthesis with up to a 15× boost in activity relative to conventional electrocatalysis. We devise a strategy to account for the effect of photothermal heating of the electrode surface, which allows the observed enhancement to be attributed to non-thermal effects such as energetic carriers and charged interfaces induced by plasmonic excitation. The synergy between electrochemical activation and plasmonic activation is the most optimal at a potential close to the onset of nitrate reduction. Plasmon-assisted electrochemistry presents an opportunity for conventional limits of electrocatalytic conversion to be surpassed due to non-equilibrium conditions generated by plasmonic excitation.