Surface voltammetric dealloying investigation on PdCu/C electrocatalysts toward ethanol oxidation in alkaline media

Voltammetric dealloying is employed here to investigate the correlations between catalytic performance and surface composition and structure, taking ethanol oxidation reaction (EOR) on Pd-Cu alloy surface as a case study. First, home-made PdCu/C with a mean particle size of ca. 3.11 ± 0.6 nm is dealloyed by repetitive potential cycling in 0.5 M H₂SO₄. With dealloying cycles rising, the Cu component is gradually leached out and the corresponding Pd/Cu atomic ratio gradually increases from ca. 2.1 to 4.0; meanwhile, SEM images display that Pd-rich porous shell is formed due to dealloying-induced surface structural rearrangement, being verified by the appearance of ear-like peaks at − 0.015 V (vs. SCE) in CVs collected in 0.5 M H₂SO₄; furthermore, XPS spectra indicate that core-level binding energies of Pd 3d_5/2 first positively shift to 336.1 eV and then oppositively move down to 334.9 eV, indicating that the d-band center of Pd composition is modulated by the dealloying treatment. Moreover, the voltammetric peak current densities for EOR follow the order of PdCu/C-DA15 > as-prepared PdCu/C ˃ > PdCu/C-DA30 ˃ commercial Pd/C ˃ PdCu/C-DA75, due to the modest downshift of Pd d-band center resulted by charge transfer and surface atomic rearrangement. In addition, the EOR durability gradually decays with the continuous loss of Cu, indicating that electro-oxidation of surface species also follows the so-called bi-functional mechanism. This work might provide some new insights into the catalysis enhancement by tuning the surface/interfacial structure of catalysts.

.