Defect-Rich CuZn Nanoparticles for Model Catalysis Produced by Femtosecond Laser Ablation

Femtosecond laser ablation of Cu0.70Zn0.30 targets in ethanol led to the formation of periodic surface nanostructures and crystalline CuZn alloy nanoparticles with defects, low-coordinated surface sites, and, controlled by the applied laser fluence, different sizes and elemental composition. The Cu/Zn ratio of the nanoparticles was determined by energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and selected area electron diffraction. The CuZn nanoparticles were about 2–3 nm in size, and Cu-rich, varying between 70 and 95%. Increasing the laser fluence from 1.6 to 3.2 J cm–2 yielded larger particles, more stacking fault defects, and repeated nanotwinning, as evident from high-resolution transmission electron microscopy, aided by (inverse) fast Fourier transform analysis. This is due to the higher plasma temperature, leading to increased random collisions/diffusion of primary nanoparticles and their incomplete ordering due to immediate solidification typical of ultrashort pulses. The femtosecond laser-synthesized often nanotwinned CuZn nanoparticles were supported on highly oriented pyrolytic graphite and applied for ethylene hydrogenation, demonstrating their promising potential as model catalysts. Nanoparticles produced at 3.2 J cm–2 exhibited lower catalytic activity than those made at 2.7 J cm–2. Presumably, agglomeration/aggregation of especially 2–3 nm sized nanoparticles, as observed by postreaction analysis, resulted in a decrease in the surface area to volume ratio and thus in the number of low-coordinated active sites.