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

Air Force Research Laboratory Materials and Manufacturing Directorate WPAFB Ohio 45433 United States

Department of Electrical Engineering and Computer Sciences Massachusetts Institute of Technology Cambridge Massachusetts 02139 United States

Department of Low Dimensional Systems J Heyrovský Institute of Physical Chemistry Academy of Sciences of the Czech Republic v v i Dolejškova 3 18223 Prague 8 Czech Republic

Department of Physics National Taiwan University Taipei 10617 Taiwan

Graduate Institute of Applied Physics National Taiwan University Taipei 10617 Taiwan

Institute of Atomic and Molecular Science Academia Sinica Taipei 10617 Taiwan

Research Center for Applied Sciences Academia Sinica Taipei 11529 Taiwan

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