RESUMO
Pulsed laser fragmentation of microparticles (MPs) in liquid is a synthesis method for producing high-purity nanoparticles (NPs) from virtually any material. Compared with laser ablation in liquids (LAL), the use of MPs enables a fully continuous, single-step synthesis of colloidal NPs. Although having been employed in several studies, neither the fragmentation mechanism nor the efficiency or scalability have been described. Starting from time-resolved investigations of the single-pulse fragmentation of single IrO2 MPs in water, the contribution of stress-mediated processes to the fragmentation mechanism is highlighted. Single-pulse, multiparticle fragmentation is then performed in a continuously operated liquid jet. Here, 2 nm-sized nanoclusters (NCs) accompanied by larger fragments with sizes ranging between several ten nm and several µm are generated. For the nanosized product, an unprecedented efficiency of up to 18 µg J-1 is reached, which exceeds comparable values reported for high-power LAL by one order of magnitude. The generated NCs exhibit high catalytic activity and stability in oxygen evolution reactions while simultaneously expressing a redox-sensitive fluorescence, thus rendering them promising candidates in electrocatalytic sensing. The provided insights will pave the way for laser fragmentation of MPs to become a versatile, scalable yet simple technique for nanomaterial design and development.
RESUMO
Pulsed laser ablation in liquids is a hierarchical multi-step process to produce pure inorganic nanoparticle colloids. Controlling this process is hampered by the partial understanding of individual steps and structure formation. In situ X-ray methods are employed to resolve macroscopic dynamics of nanosecond PLAL as well to analyse the distribution and speciation of ablated species with a microsecond time resolution. High time resolution can be achieved by synchrotron-based methods that are capable of 'single-shot' acquisition. X-ray multicontrast imaging by a Shack-Hartmann setup (XHI) and small angle X-ray scattering (SAXS) resolve evolving nanoparticles inside the transient cavitation bubble, while X-ray absorption spectroscopy in dispersive mode opens access to the total material yield and the chemical state of the ejecta. It is confirmed that during ablation nanoparticles are produced directly as well as reactive material is detected, which is identified in the early stage as Zn atoms. Nanoparticles within the cavitation bubble show a metal signature, which prevails for milliseconds, before gradual oxidation sets in. Ablation is described by a phase explosion of the target coexisting with full evaporation. Oxidation occurs only as a later step to already formed nanoparticles.
RESUMO
The synthesis of chemically clean and environmentally friendly nanoparticles through pulsed laser ablation in liquids has shown a number of advantages over conventional chemical synthesis methods and has evolved into a thriving research field attracting laboratory and industrial applications. The fundamental understanding of processes leading to the nanoparticle generation, however, still remains elusive. In particular, the origin of bimodal nanoparticle size distributions in femto- and picosecond laser ablation in liquids, where small nanoparticles (several nanometers) with narrow size distribution are commonly observed to coexist with larger (tens to hundreds of nanometers) ones, has not been explained so far. In this paper, joint computational and experimental efforts are applied to understand the mechanisms of nanoparticle formation in picosecond laser ablation in liquids and to explain the bimodal nanoparticle size distributions. The results of a large-scale atomistic simulation reveal the critical role of the dynamic interaction between the ablation plume and the liquid environment, leading to the generation of large nanoparticles through a sequence of hydrodynamic instabilities at the plume-liquid interface and a concurrent nucleation and growth of small nanoparticles in an expanding metal-liquid mixing region. The computational predictions are supported by a series of stroboscopic videography experiments showing the emergence of small satellite bubbles surrounding the main cavitation bubble generated in single pulse experiments. Carefully timed double pulse irradiation triggers expansion of secondary cavitation bubbles indicating, in accord with the simulation results, the presence of localized sites of laser energy deposition (possibly large nanoparticles) injected into the liquid at the early stage of the bubble formation.
RESUMO
During laser synthesis of colloids, cavitation bubbles with lifetimes in the microsecond-scale form and shield the laser pulse leading to a decrease in nanoparticle output. A second type of productivity-limiting bubble that severely affects the productivity of the process is often neglected. With lifetimes from milliseconds to seconds, these persistent bubbles are systematically studied in this work by quantifying their composition, amount, size and dwell time in liquids with different viscosities and by relating the results to the nanoparticle productivities. It is found that during synthesis in water, water splitting occurs leading to persistent bubbles consisting of hydrogen and oxygen. In glycols, hydrogen and molecular carbon species containing microbubbles are formed. These persistent microbubbles shield up to 65% of the incoming laser beam depending on the liquid as well as the laser fluence and require attention by means of reducing their dwell time in the ablation zone and enhancing the nanoparticle output by liquid flow. The highest productivities and monodisperse quality are achieved in liquids with the lowest viscosities.
RESUMO
Utilizing a novel laser system consisting of a 500 W, 10 MHz, 3 ps laser source which is fully synchronized with a polygon scanner reaching scanning speeds up to 500 m/s, we explore the possibilities to increase the productivity of nanoparticle synthesis by laser ablation in liquids. By exploiting the high scanning speed, laser-induced cavitation bubbles are spatially bypassed at high repetition rates and continuous multigram ablation rates up to 4 g/h are demonstrated for platinum, gold, silver, aluminum, copper, and titanium. Furthermore, the applicable, ablation-effective repetition rate is increased by two orders of magnitude. The ultrafast ablation mechanisms are investigated for different laser fluences, repetition rates, interpulse distances, and ablation times, while the resulting trends are successfully described by validating a model developed for ultrafast laser ablation in air to hold in liquids as well.
RESUMO
The synthesis of catalysis-relevant nanoparticles such as platinum and gold is demonstrated with productivities of 4 g h(-1) for pulsed laser ablation in liquids (PLAL). The major drawback of low productivity of PLAL is overcome by utilizing a novel ultrafast high-repetition rate laser system combined with a polygon scanner that reaches scanning speeds up to 500 m s(-1). This high scanning speed is exploited to spatially bypass the laser-induced cavitation bubbles at MHz-repetition rates resulting in an increase of the applicable, ablation-effective, repetition rate for PLAL by two orders of magnitude. The particle size, morphology and oxidation state of fully automated synthesized colloids are analyzed while the ablation mechanisms are studied for different laser fluences, repetition rates, interpulse distances, ablation times, volumetric flow rates and focus positions. It is found that at high scanning speeds and high repetition rate PLAL the ablation process is stable in crystallite size and decoupled from shielding and liquid effects that conventionally occur during low-speed PLAL.
RESUMO
Size control of laser-fabricated surfactant-free gold nanoparticles is a challenging endeavor. In this work, we show that size control can be achieved by adding ions with low salinity during synthesis. In addition, this approach offers the opportunity to fundamentally study ion interactions with bare nanoparticle surfaces and can help to elucidate the nanoparticle formation mechanism. The studies were carried out in a flow-through reactor and in the presence of NaCl, NaBr and sodium phosphate buffer at minimal ionic strengths. A significant size quenching effect at ionic strengths from 1-50 µM was found, which allowed surfactant-free nanoparticle size control with average diameters of 6-30 nm. This effect went along with low polydispersity and minimal aggregation tendencies and was confirmed by UV-vis spectroscopy, TEM, SEM and analytical disk centrifugation. Our findings indicate that size quenching originates from an anionic electrostatic stabilization depending on the nanoparticle surface area, which may be caused by specific ion adsorption. By subsequent delayed bioconjugation in liquid-flow using bovine serum albumin as a stabilizing agent, nano-bioconjugates with good stability in cell culture media were obtained, which are applicable in toxicology and cell biology.
Assuntos
Eletrólitos/química , Ouro/química , Lasers , Nanopartículas Metálicas/química , Nanotecnologia/métodos , Tamanho da Partícula , Soroalbumina Bovina/química , Animais , Bovinos , Estabilidade de Medicamentos , Concentração Osmolar , Tensoativos/químicaRESUMO
Using wires of defined diameters instead of a planar target for pulsed laser ablation in liquid results in significant increase of ablation efficiency and nanoparticle productivity up to a factor of 15. We identified several competitive phenomena based on thermal conductivity, reflectivity and cavitation bubble shape that affect the ablation efficiency when the geometry of the target is changed. On the basis of the obtained results, this work represents an intriguing starting point for further developments related to the up-scaling of pulsed laser ablation in liquid environments at the industrial level.