Light-driven methane dry reforming with single atomic site antenna-reactor plasmonic photocatalysts

Syngas is a mixture of CO and H-2 that can be converted into a variety of fuels. Syngas can be produced thermocatalytically from CH4 and CO2, but this requires high temperatures and coke formation can be a problem. Here the authors demonstrate lower temperature, light-driven production of syngas using a coke-resistant plasmonic photocatalyst. Syngas, an extremely important chemical feedstock composed of carbon monoxide and hydrogen, can be generated through methane (CH4) dry reforming with CO2. However, traditional thermocatalytic processes require high temperatures and suffer from coke-induced instability. Here, we report a plasmonic photocatalyst consisting of a Cu nanoparticle 'antenna' with single-Ru atomic 'reactor' sites on the nanoparticle surface, ideal for low-temperature, light-driven methane dry reforming. This catalyst provides high light energy efficiency when illuminated at room temperature. In contrast to thermocatalysis, long-term stability (50 h) and high selectivity (>99%) were achieved in photocatalysis. We propose that light-excited hot carriers, together with single-atom active sites, cause the observed performance. Quantum mechanical modelling suggests that single-atom doping of Ru on the Cu(111) surface, coupled with excited-state activation, results in a substantial reduction in the barrier for CH4 activation. This photocatalyst design could be relevant for future energy-efficient industrial processes.