Metal Oxide Nanoparticle Preparation by Pulsed Laser Ablation of Metallic Targets in Liquid

The basic mechanisms of pulsed laser ablation in liquids (PLAL) as a method for the synthesis of nanoparticles (NPs) were considered. Physical and chemical processes occurring during the PLAL that determine the formation, composition and structure of the nanoparticles obtained are described. The influence of the composition and properties of the target material, the solvent and the characteristics of the laser irradiation on the efficiency of the synthesis of nanoparticles is discussed. Separately, an influence of the absorption and scattering (including nonlinear) of laser radiation in the dispersion of nanoparticles on the primary synthetic processes and secondary transformations inside the colloidal solution is examined. The specificity of the characterization of the colloidal solutions of oxide particles produced by PLAL is highlighted. The most promising practical applications of nanomaterials obtained are identified and the examples of their successful use in catalytic research and biomedicine are provided

Potential of sub-THz-wave generation in Li2B4O7 nonlinear crystal at room and cryogenic temperatures

Due to their high optical damage threshold, borate crystals can be used for the efficient nonlinear down-conversion of terawatt laser radiation into the terahertz (THz) frequency range of the electromagnetic spectrum. In this work, we carried out a thorough study of the terahertz optical properties of the lithium tetraborate crystal (Li2B4O7; LB4) at 295 and 77 K. Approximating the terahertz refractive index in the form of Sellmeier’s equations, we assessed the possibility of converting the radiation of widespread high-power laser sources with wavelengths of 1064 and 800 nm, as well as their second and third harmonics, into the THz range. It was found that four out of eight types of three-wave mixing processes are possible. The conditions for collinear phase matching were fulfilled only for the o - e -o type of interaction, while cooling the crystal to 77 K did not practically affect the phase-matching curves. However, a noticeable increase of birefringence in the THz range with cooling (from 0.12 to 0.16) led to an increase in the coherence length for o-o-e and e-e-e types of interaction, which are potentially attractive for the down-conversion of ultrashort laser pulses

Dielectric properties of BiB3O6 crystal in the sub-THz range

We present the thorough studies of dielectric properties of BiB3O6 (BIBO) crystal in the sub-THz range. We observe a large birefringence Δn = nZ −nX = 1.5 and the values of absorption coefficients of all three axes to be less than 0.5 cm−1. The difference from visible range in angle ϕ between the axes z and X is found to be more than 6°. The simulated phase-matching curves show the optimal value of the angle θ to be around 25.5°±1° for an efficient millimeter-wave generation under the pump of 1064 nm laser radiation

Millimetre-wave range optical properties of BIBO

We present the thorough studies of optical properties of BiB3O6 (BIBO) crystal in the millimeter-wave (subterahertz) range. We observe a large birefringence Δn = nZ −nX = 1.5 and the values of absorption coefficients of all three axes to be less than 0.5 cm−1 at the frequency of 0.3 THz. The difference from visible range in angle ϕ between the dielectric axis z and crystallophysical axis X is found to be more than 6°. The simulated phase-matching curves in the xz plane of the crystal show the optimal value of the angle θ to be around 25.5°±1° for an efficient millimeter-wave generation under the pump of 1064 nm laser radiation

In situ probing of Pt/TiO2_{2} activity in low-temperature ammonia oxidation

The improvement of the low-temperature activity of the supported platinum catalysts in selective ammonia oxidation to nitrogen is still a challenging task. The recent developments in in situ/operando characterization techniques allows to bring new insight into the properties of the systems in correlation with their catalytic activity. In this work, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando X-ray absorption spectroscopy (XAS) techniques were applied to study Pt/TiO$_{2}$ catalysts in ammonia oxidation (NH$_{3}$ + O$_{2}$ reaction). Several synthesis methods were used to obtain samples with different size of Pt particles, oxidation state of Pt, and morphology of the support. Metal platinum particles on titania prepared by pulsed laser ablation in liquids exhibited the highest activity at lower temperatures with the temperature of 50% conversion of NH$_{3}$ being 150 °C. The low-temperature activity of the catalysts synthesized by impregnation can be improved by the reductive pretreatment. NAP-XPS and operando XANES data do not show formation of PtO$_{x}$ surface layers or PtO/PtO$_{2}$ oxides during NH$_{3}$ + O$_{2}$ reaction. Despite the differences in the oxidation state of platinum in the as-prepared catalysts, their treatment in the reaction mixture results in the formation of metallic platinum particles, which can serve as centers for stabilization of the adsorbed oxygen species. Stabilization of the bulk platinum oxide structures in the Pt/TiO$_{2}$ catalysts seems to be less favorable due to the metal–support interaction

Optical properties of β-BBO and potential for THz applications

The anisotropy of optical properties of high quality beta barium borate crystal (β-BaB2O4, β-BBO) was studied in the main transparency window by using classic spectroscopic methods and in the range of 0.2 – 2 THz by using THz time-domain spectroscopy. β-BBO crystals were grown by the top-seeded solution technique in a highly resistive furnace with a heat field of 3-fold axis symmetry. At room temperature (RT), absorption coefficient in the maximal transparency window in grown crystals did not exceed 0.05 cm-1. Strong absorption anisotropy was observed in 3 – 5 μm and the THz range. At 1 THz absorption coefficients for e and o wave were, respectively, 7 cm-1 and 21 cm-1 at RT; 2 cm-1 and 10 cm-1 at 81 K. At the most attractive for out-of-door applications range < 0.4 THz the absorption coefficient is found to be very low: below 0.2 cm-1 at RT and 1 cm-1 at 81 K. Refractive indices dispersions measured by THz-TDS were approximated in the form of Sellmeier equations. Birefringence is found quite large for phase matched difference frequency generation (DFG) or down-conversion into the THz range (THz-DFG) under near IR pump at RT and 81 K. Type II (oe-o and eo-o), and type I (ee-e) three wave interactions can be realized at RT. THz-DFG of Nd:YAG laser and KTP OPO can be realized by type II (oe-o) three-wave interaction. For selected spectral ranges of femtosecond Ti:Sapphire laser efficient phase matched and group velocity matched optical rectification can be realized by another two types of three wave interactions. Accounting other well-known attractive physical properties of β-BBO crystal, wide application in THz technique can be forecasted

Phase and Structural Thermal Evolution of Bi–Si–O Catalysts Obtained via Laser Ablation

Laser methods are successfully used to prepare complex functional nanomaterials, especially for biomedicine, optoelectronics, and heterogeneous catalysis. In this paper, we present complex oxide and composite nanomaterials based on Bi and Si produced using laser ablation in liquid followed by subsequent powder annealing. Two synthesis approaches were used, with and without laser post-treatment of mixed (in an atomic ratio of 2:1) laser-generated Bi and Si colloids. A range of methods were used to characterize the samples: UV-Vis diffusion reflection, IR and Raman spectroscopy, synchronous thermal analysis, X-ray diffraction, transmission electron microscopy, as well as specific surface-area evaluation. We also followed the dynamics of phase transformations, as well as composition, structure and morphology of annealed powders up to 800 °C. When heated, the non-irradiated series of samples proceeded from metallic bismuth, through β-Bi2O3, and resulted in bismuth silicates of various stoichiometries. At the same time, in their laser-irradiated counterparts, the formation of silicates proceeded immediately from the amorphous Bi2SiO5 phase formed after laser treatment of mixed Bi and Si colloids. Finally, we show their ability to decompose persistent organic molecules of Rhodamine B and phenol under irradiation with a soft UV (375 nm) source

Photocatalytic Decomposition of Rhodamine B and Selective Oxidation of 5-Hydroxymethylfurfural by β-Bi₂O₃/Bi₁₂SiO₂₀ Nanocomposites Produced by Laser

In this work, we studied the catalytic performance of a β-Bi2O3/Bi12SiO20 nanocomposite material in the reactions involving the photodecomposition of rhodamine B and selective photooxidation of 5-hydroxymethylfurfural (HMF). The semiconductor composite nanomaterial was obtained by means of the mechanical grinding of a mixture of nanopowders of β-Bi2O3 and sillenite, both individually produced via pulsed laser ablation. The crystal structure of the prepared composite particles was confirmed by means of X-ray diffraction, while the optical properties of both individual components and their composite (with different ratios of Bi2O3 and Bi12SiO20) were also studied. The photocatalytic activity of the composite particles was studied in the course of their decomposition of rhodamine B under LED excitation at wavelengths of 375, 410 and 470 nm. It was shown that the optimal β-Bi2O3/Bi12SiO20 ratio in the composite particles resulted in their photocatalytic activity exceeding those of both single-phase β-Bi2O3 and Bi12SiO20, as well as that of their mixtures (by ~2.3 times for the excitation of an LED with λ = 375 nm). The novel composite particles were also found to perform better in the selective photocatalytic oxidation of HMF: at a conversion of ~5%, the selectivity toward DFF of the nanocomposite was significantly higher (10.3%) than that of sample Bi2O3 (−4.2%). A model was proposed that explains the increase in activity of the newly prepared photocatalyst due to the formation of a type II heterojunction in its particles