The development of highly efficient electrocatalysts for the ethanol oxidation reaction (EOR) is essential for the commercialization of direct ethanol fuel cells, yet challenges remain. In this study, a one-pot solution-phase method to synthesize Pd nanowire networks (NNWs) with very high surface-to-volume ratio having numerous twin and grain boundaries is developed. Using the same method, the Pd lattice is further engineered by introducing Ag and Cu atoms to produce AgPd, and CuPd alloy structure which significantly shifts the Pd d-band center upward and downward, respectively due to strain and ligand effects. Theoretical analysis employing density functional theory (DFT) demonstrates that such modification of the d-band center significantly influences the adsorption energies of reactants on the catalytic surface. Owing to their notably high surface-to-volume ratio and the presence of multiple twin and grain boundaries, Pd NNWs demonstrate significantly enhanced electrocatalytic activity toward EOR, ≈7.2 times greater than that of commercial Pd/C. Remarkably, compared to Pd NNWs, AgPd, and CuPd NNWs display enlarged and reduced electrocatalytic activity toward EOR, respectively. Specifically, Ag4Pd7 NNWs achieve a remarkable mass activity of 9.00 A mgpd -1 for EOR, which is 13.6 times higher than commercial Pd/C.
The direct alcohol fuel cells (DAFCs) rely on alcohol oxidation reactions (AORs) to produce electricity, which require catalysts with optimized electronic structure to accelerate the sluggish AORs. Herein, an epitaxial growth of Pd layer onto the pentatwinned Au@Ag core-shell nanorods (NRs) is reported to synthesize highly strained Au@AgPd core-shell NRs. The tensile strain in the AgPd shell of the Au@AgPd nanorods (NRs) arises not only from the core-shell lattice mismatch but also from twinning and lattice distortion occurring at the five twinned boundaries present in the structure. Theoretical simulations prove that the presence of tensile strains in the AgPd layer leads to a significant upward shift of the d-band center of the Pd site toward the Fermi level which remarkably changes the adsorption energy of alcohols on the surface. Highly strained Au@AgPd NRs show exceptional mass activities in electrochemical oxidation of biomass-derived alcohols (ethylene glycol, ethanol, and glycerol) reaching up to 18.66, 15.6, and 7.90 A mgpd -1 , respectively. These values are 23.3, 23.6, and 23.2 times higher than commercial Pd/C catalysts. This strain engineering strategy set the platform for the design and synthesis of highly efficient and versatile catalysts for the construction of high-performance DAFCs.
