Surface strain-regulated interfacial catalysis in Pd3Pb nanosheets for enhanced C1-pathway ethanol electrooxidation.

Intermetallic palladium-based nanomaterials hold great promise for alcohol electrooxidation, but the role of surface topography in governing interfacial catalytic processes remains underexplored. Herein, we report a comparative investigation of intermetallic Pd3Pb nanosheets with flat and crumpled surface topographies, where the crumpled morphology is achieved by introducing N-(octadec-9-en-1-yl)diethanolamine during synthesis, while flat nanosheets are obtained in its absence. For ethanol oxidation, the crumpled Pd3Pb nanosheets deliver a mass activity of 1742.9 mA mg-1 and retain 10.0 mA cm-2 after 100 cycles, substantially outperforming flat nanosheets (1192.8 mA mg-1, 3.4 mA cm-2) and commercial Pd/C (709.2 mA mg-1, 1.1 mA cm-2). In situ Raman spectroscopy reveals that the reaction proceeds predominantly via the C1 pathway, evidencing efficient C-C bond cleavage on the crumpled surface. By using density functional theory simulations this enhancement can be attributed to localized surface strain induced by the crumpled topography-modeled on the Pd3Pb(311) surface-which upshifts the d-band center to -1.53 eV and strengthens *OH binding (-3.29 eV), thereby optimizing intermediate adsorption energetics and facilitating the oxidative removal of carbonaceous poisons. This work provides a synthetic route to engineer crumpled surface topography in intermetallic nanosheets and demonstrates its critical role in regulating interfacial catalysis for C1-selective alcohol electrooxidation.