Controlling catalytic selectivity on metal nanoparticles by direct photoexcitation of adsorbate-metal bonds

Engineering heterogeneous metal catalysts for high selectivity in thermal driven reactions typically involves the synthesis of nanostructures with well-controlled geometries and compositions. However, inherent relationships between the energetics of elementary steps limit the control of catalytic selectivity through these approaches. Photon excitation of metal catalysts can induce chemical reactivity channels that cannot be accessed using thermal energy, although the potential for targeted activation of adsorbate-metal bonds is limited because the processes of photon absorption and adsorbate-metal bond photoexcitation are typically separated spatially. Here, we show that the use of sub-5-nanometer metal particles as photocatalysts enables direct photoexcitation of hybridized adsorbate-metal states as the dominant mechanism driving photochemistry. Activation of targeted adsorbate-metal bonds through direct photoexcitation of hybridized electronic states enabled selectivity control in preferential CO oxidation in H₂ rich streams. This mechanism opens new avenues to drive selective catalytic reactions that cannot be achieved using thermal energy.