The\nImportance of Catalytic Effects in Hot-Electron-Driven\nChemical Reactions

Hot electrons (HEs)\nrepresent out-of-equilibrium carriers that\nare capable of facilitating reactions which are inaccessible under\nconventional conditions. Despite the similarity of the HE process\nto catalysis, optimization strategies such as orbital alignment and\nadsorption kinetics have not received significant attention in enhancing\nthe HE-driven reaction yield. Here, we investigate catalytic effects\nin HE-driven reactions using a compositional catalyst modification\n(CCM) approach. Through a top-down alloying process and systematic\ncharacterization, using electrochemical, photodegradation, and ultrafast\nspectroscopy, we are able to disentangle chemical effects from competing\nelectronic phenomena. Correlation between reactant energetics and\nthe HE reaction yield demonstrates the crucial role of orbital alignment\nin HE catalytic efficiency. Optimization of this parameter was found\nto enhance HE reaction efficiency 5-fold, paving the way for tailored\ndesign of HE-based catalysts for sustainable chemistry applications.\nFinally, our study unveils an emergent ordering effect in photocatalytic\nHE processes that imparts the catalyst with an unexpected polarization\ndependence.