Farheen KhurshidJeyavelan MuthuYen-Yu WangYao-Wei WangMu-Chen ShihDing-Rui ChenYu-Jung LuDrake AustinNicholas GlavinJan PlšekMartin KalbáčYa-Ping HsiehMario Hofmann2025-01-092025-01-092024-12-04https://scholars.lib.ntu.edu.tw/handle/123456789/724689Hot 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.Bimetallic AlloyCompositional Catalyst ModificationGradientHot-ElectronPhotocatalysis[SDGs]SDG3journal article10.1021/acsnano.4c12923