P-block metal-induced charge redistribution and lattice strain assisting CC bond cleavage and anti‑carbon monoxide poisoning in ethanol electrooxidation.

The ability to cleave the CC bond plays a critical role in determining the selectivity of the ethanol electrooxidation reaction toward either the C1 or C2 pathway. In this work, we successfully synthesized a series of dumbbell-shaped ternary PdBiTe alloy nanocrystals via a visible light-assisted method and tuned the lattice strain by varying the Pd content. Among the samples, PdBiTe-3-with an optimal tensile strain of approximately 3.6 %-exhibited the highest intrinsic activity (11.77 mA cm) and mass activity (11.48 A mg) in ethanol oxidation reaction (EOR), which are 4.04 and 7.41 times higher, respectively, than those of commercial Pd/C. We found that a series of ternary PdBiTe alloy catalysts could adhere well to the Sabatier principle, the optimized PdBiTe-3 exhibited a more suitable d-band center which balanced the binding strength with reaction intermediates, thereby demonstrating enhanced resistance to CO and accelerating the EOR process. In-situ Fourier transform infrared spectroscopy and proton nuclear magnetic resonance measurements confirmed that PdBiTe-3 facilitates more efficient CC bond cleavage, thereby enhancing selectivity toward the C1 pathway. Density functional theory calculations further revealed that the incorporation of p-block metals (Bi and Te) induces charge redistribution on the Pd atoms of the PdBiTe-3 surface and significantly reduces the energy barrier for CO oxidation. This enables a more continuous and efficient EOR process on the PdBiTe-3 surface catalyst.