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.

Highly Stable Self-Cleaning Paints Based on Waste-Valorized PNC-Doped TiO2 Nanoparticles.

Adding photocatalytically active TiO2 nanoparticles (NPs) to polymeric paints is a feasible route toward self-cleaning coatings. While paint modification by TiO2-NPs may improve photoactivity, it may also cause polymer degradation and release of toxic volatile organic compounds. To counterbalance adverse effects, a synthesis method for nonmetal (P, N, and C)-doped TiO2-NPs is introduced, based purely on waste valorization. PNC-doped TiO2-NP characterization by vibrational and photoelectron spectroscopy, electron microscopy, diffraction, and thermal analysis suggests that TiO2-NPs were modified with phosphate (P=O), imine species (R=N-R), and carbon, which also hindered the anatase/rutile phase transformation, even upon 700 °C calcination. When added to water-based paints, PNC-doped TiO2-NPs achieved 96% removal of surface-adsorbed pollutants under natural sunlight or UV, paralleled by stability of the paint formulation, as confirmed by micro-Fourier transform infrared (FTIR) surface analysis. The origin of the photoinduced self-cleaning properties was rationalized by three-dimensional (3D) and synchronous photoluminescence spectroscopy, indicating that the dopants led to 7.3 times stronger inhibition of photoinduced e-/h+ recombination when compared to a benchmark P25 photocatalyst.

Formation of Periodic Surface Structures by Multipulse Femtosecond Laser Processing of Au-Coated Ni in Various Fluids.

Using multipulse linearly polarized femtosecond laser processing of a Au-coated Ni surface in various liquid media created subwavelength self-organized nanoripples. The thin gold film improved the laser absorptivity, decreasing the ripple generation threshold in liquids. High spatial frequency ripples exhibited lower angular deviation than low spatial frequency ones, but in water the deviation was comparable for both types of ripples. The initiation of nanoripples may precede nanoparticle generation, which is why in hexane several cuboid Au particles were trapped between the ripples. Fast cooling processes freeze ejected molten droplets during the phase explosion and surface reorganization. Grazing incidence X-ray diffraction of samples processed in butanol showed a small shift toward smaller angles for the Ni phase, indicating a lattice expansion due to higher tensile stress. Confocal micro-Raman spectroscopy detected surface graphitization and amorphization in areas laser-treated in ethanol, butanol, and hexane, with the highest carbonization observed in butanol. Presumably, femtosecond laser-induced photolysis triggers the formation of graphite nanocrystallites, and consecutive pulses cause amorphization. Static contact angle measurements showed a general tendency toward hydrophobicity with highest contact angles for rippled areas created in butanol.

Near-Infrared Femtosecond Laser Ablation of Au-Coated Ni: Effect of Organic Fluids and Water on Crater Morphology, Ablation Efficiency and Hydrodynamic Properties of NiAu Nanoparticles.

Scanning electron microscopy (SEM) and profilometry of the crater morphology and ablation efficiency upon femtosecond laser ablation of Au-coated Ni targets in various fluids revealed a pronounced dependence on the ablation medium. For ethanol, a sufficient ablation efficiency was obtained, whereas for 2-butanol a higher efficiency indicated stronger laser-target interaction. Hierarchical features in the crater periphery pointed to asymmetrical energy deposition or a residual effect of the Coulomb-explosion-initiating ablation. Significant beam deviation in 2-butanol caused maximum multiple scattering at the crater bottom. The highest values of microstrain and increased grain size, obtained from Williamson-Hall plots, indicated the superposition of mechanical stress, defect formation and propagation of fatigue cracks in the crater circumference. For n-hexane, deposition of frozen droplets in the outer crater region suggested a femtosecond-laser-induced phase explosion. A maximum ablation depth occurred in water, likely due to its high cooling efficiency. Grazing incidence micro X-ray diffraction (GIXRD) of the used target showed residual carbon and partial surface oxidation. The produced nanoparticle colloids were examined by multiangle dynamic light scattering (DLS), employing larger scattering angles for higher sensitivity toward smaller nanoparticles. The smallest nanoparticles were obtained in 2-butanol and ethanol. In n-hexane, floating carbon flakes originated from femtosecond-laser-induced solvent decomposition.

The influence of the fluid nature on femtosecond laser ablation properties of a SiO2/Si target and synthesis of ultrafine-grained Si nanoparticles.

Nanocrystalline silicon nanoparticles with a median crystallite size of 3-4 nm and several crystalline phases and defects (e.g. twin boundary) were produced by femtosecond laser processing of a SiO2/Si target in various organic fluids. Furthermore, a nanoscaled amorphous oxide layer and a few atomic layers of a graphite shell were detected in ethanol and 2-butanol correspondingly. The ultrafast laser pulses may manipulate nanostructures at the atomic level and generate a high density of defects; this may be correlated with significant thermal stresses on nanoparticles and rapid condensation of primary nanoparticles with high cooling rates. Size distribution width and a polydispersity index slightly increased with increasing laser fluence in ethanol. In 2-butanol, the maximum ablation volume was observed. The specific ablation rates in 2-butanol and ethanol were approximately five times higher than n-hexane. The lowest ablation efficiency in n-hexane can be associated with femtosecond laser-induced photolysis and pyrolysis of solvent molecules, as total energy deposition on the material may be reduced due to the formation of carbonaceous products. The roughened zones (average roughness of ∼400 nm) in circumferences of the ablated craters in 2-butanol may be related to a correlation between the erosive power of the vapour bubble collapse and higher pressure at the bubble wall in relatively high dynamic viscosity fluids. Furthermore, sputtering of a pristine surface by releasing nanoparticles from the collective collapse of up-flow vapour bubbles can also contribute to the generation of roughened regions.

Laser-Assisted Synthesis of Colloidal FeWx Oy and Fe/Fex Oy Nanoparticles in Water and Ethanol.

Homogeneous polycrystalline Fex Oy nanoparticles were generated by ablation of iron targets in water by nanosecond laser pulses at 532 nm. In ethanol, crystalline core-shell Fe/Fex Oy structures with size medians around 20 nm were produced. The ablation of FeWx Oy targets in water resulted in crystalline hollow shells and homogeneous FeWx Oy nanoparticles. In contrast, amorphous core-shell FeWx Oy nanoparticles with a median size of 17 nm were produced in ethanol. The size distribution of both the Fex Oy and the FeWx Oy particles showed a slight dependence on fluence and pulse number. This may be related to primary and secondary ablation and modification mechanisms.

Laser-Assisted Synthesis of Colloidal Ni/NiOx Core/Shell Nanoparticles in Water and Alcoholic Solvents.

The nanosecond-pulse laser-assisted generation of Ni/NiOx core/shell nanoparticles (NPs) in water and alcoholic fluids can yield colloidal solutions without surfactants. The size distribution can be controlled by the nature of the alcohol, the number of laser pulses and the laser fluence. The incubation of the nickel target ablation in liquid contact shows a dependence on the carbon number of the respective alcohol. The laser-generated NPs consist of crystalline nickel cores with face-centred cubic patterns and stacking fault defects surrounded by nickel oxide shells. The solvent butanol, in contrast to ethanol and isopropanol, yields a narrow, nearly unimodal, size distribution. The majority of NPs have low size distributions, with medians in the range of 10-20 nm. These can be related to a metal ablation plume interacting with a supercritical liquid that decelerates the ejected material in a low-density metal-water mixing region. NPs in the range above 30 nm result in a minority distribution tail that strongly depends on the fluid nature, the pulse number and the fluence. This coarse NP set may be correlated with the rupture of a superheated molten-metal layer into larger entities.