Precise Modulation of Surface Pb-Rich Intermetallic Pd3Pb Nanocubes for Efficient Electrocatalytic CO2 Reduction

• • Surface Pb-rich Pd3Pb/Pb nanocubes achieve a Faradaic efficiency of 96.88% for C1+ products at −0.72 V vs. RHE, outperforming Pd3Pb/Pd (39.86%) and standard Pd3Pb (81.75%), demonstrating a 2.4-fold improvement over Pd-rich surfaces. • • The 20 nm intermetallic nanocubes with tunable Pb exposure enable isolation of ligand effects from geometric factors, providing a model system for structure-activity correlation studies. • • DFT calculations reveal that Pb incorporation upshifts the d-band center of Pd via p-d hybridization, strengthening intermediate adsorption and lowering energy barriers for C1+ pathways while suppressing HER. • • The synthetic method (one-step solvothermal) yields well-defined nanocubes with controlled surface Pb content, offering a scalable route for precise surface engineering of intermetallic electrocatalysts.