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Plasmonically generated hot electrons hold significant promise as nonthermal energy sources for driving chemical transformations, yet their catalytic efficacy is fundamentally constrained by the intrinsic Fermi level ( E F ) limitations of noble metals. Using palladium (Pd) as a model system─a material renowned for its exceptional catalytic activity but restricted by its low E F (≈ −5.1 eV)─we demonstrate a rational interfacial engineering strategy to amplify hot electron energy and reaction performance. By integrating copper (Cu) into Pd nanostructures, we achieve a 0.45–75 eV elevation in hot electron energy through tailored Cu–Pd interfacial electronic modulation. This advancement unlocks previously inaccessible reaction pathways, most notably enabling a direct four-electron reduction process on CuPd Janus nanoparticles synthesized via in situ Cu growth on Pd(111) surfaces, a mechanism absent in pure Pd systems. Furthermore, the introduction of Pd (100) facets synergistically enhances catalytic efficiency, elevating Suzuki coupling conversion from 65 to 94% while achieving a 1.6-fold acceleration in reaction kinetics. Combining in situ electrochemical surface-enhanced Raman spectroscopy and theoretical calculations, we quantify that the hot electron energy level of Pd increases from −5.11 to −4.66 eV, with an increase of 0.45 eV, thereby optimizing hot electron transfer dynamics and redox potentials. This work provides a paradigm-shifting approach to plasmonic photocatalyst design, emphasizing dual control over hot electron energetics and interfacial charge transfer pathways as critical levers for overcoming inherent material limitations in energy-conversion applications.
Cao et al. (Mon,) studied this question.