Light-Driven\nDehydrogenation of Propane Using Plasmonic\nAl@TiO<sub>2</sub> Core–Shell Nanoparticles with Pt Single\nAtoms and Clusters

Non-oxidative dehydrogenation of\npropane produces valuable\npropylene\nfeedstocks and clean hydrogen fuel but, as an endothermic reaction,\nconventionally requires high temperatures. Here we report a photocatalyst\nthat combines plasmonic Al@TiO<sub>2</sub> core–shell nanoparticles\nwith Pt single atomic active sites and clusters, capable of efficient\ndehydrogenation of propane into propylene with high selectivity using\nvisible light illumination. Through strong metal–support interactions,\nthe reducible TiO<sub>2</sub> shell layer controls the nuclearity\nof the exposed Pt species, which in turn controls their photocatalytic\nreactivity. A comparison of reaction orders for the light-driven and\nthe corresponding thermally driven process shows that hot carriers\nlower the apparent C−H activation energy barrier. Plasmon-generated\nhot carriers, along with the presence of low-coordination Pt sites,\nsuppress further dehydrogenation of propylene and prevent coke formation\nthat would otherwise occur on extended Pt islands. This work clearly\ndemonstrates how plasmonics and single atom catalysts can be combined\nfor high-specificity photocatalyst design.