Physical Regimes and Mechanisms of Picosecond Laser Fragmentation of Gold Nanoparticles in Water from X-ray Probing and Atomistic Simulations.

Laser fragmentation in liquids has emerged as a promising green chemistry technique for changing the size, shape, structure, and phase composition of colloidal nanoparticles, thus tuning their properties to the needs of practical applications. The advancement of this technique requires a solid understanding of the mechanisms of laser-nanoparticle interactions that lead to the fragmentation. While theoretical studies have made impressive practical and mechanistic predictions, their experimental validation is required. Hence, using the picosecond laser fragmentation of Au nanoparticles in water as a model system, the transient melting and fragmentation processes are investigated with a combination of time-resolved X-ray probing and atomistic simulations. The direct comparison of the diffraction profiles predicted in the simulations and measured in experiments has revealed a sequence of several nonequilibrium processes triggered by the laser irradiation. At low laser fluences, in the regime of nanoparticle melting and resolidification, the results provide evidence of a transient superheating of crystalline nanoparticles above the melting temperature. At fluences about three times the melting threshold, the fragmentation starts with evaporation of Au atoms and their condensation into small satellite nanoparticles. As fluence increases above five times the melting threshold, a transition to a rapid (explosive) phase decomposition of superheated nanoparticles into small liquid droplets and vapor phase atoms is observed. The transition to the phase explosion fragmentation regime is signified by prominent changes in the small-angle X-ray scattering profiles measured in experiments and calculated in simulations. The good match between the experimental and computational diffraction profiles gives credence to the physical picture of the cascade of thermal fragmentation regimes revealed in the simulations and demonstrates the high promise of the joint tightly integrated computational and experimental efforts.

Photomechanical Laser Fragmentation of IrO2 Microparticles for the Synthesis of Active and Redox-Sensitive Colloidal Nanoclusters.

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.

Ultrafast cold-brewing of coffee by picosecond-pulsed laser extraction.

Coffee is typically brewed by extracting roasted and milled beans with hot water, but alternative methods such as cold brewing became increasingly popular over the past years. Cold-brewed coffee is attributed to health benefits, fewer acids, and bitter substances. But the preparation of cold brew typically needs several hours or even days. To create a cold-brew coffee within a few minutes, we present an approach in which an ultrashort-pulsed laser system is applied at the brewing entity without heating the powder suspension in water, efficiently extracting caffeine and aromatic substances from the powder. Already 3 min irradiation at room temperature leads to a caffeine concentration of 25 mg caffeine per 100 ml, comparable to the concentrations achieved by traditional hot brewing methods but comes without heating the suspension. Furthermore, the liquid phase's alkaloid content, analyzed by reversed-phase liquid chromatography coupled to high-resolution mass spectrometry, is dominated by caffeine and trigonelline and is comparable to traditional cold-brewed coffee rather than hot-brewed coffee. Furthermore, analyzing the head-space of the prepared coffee variants, using in-tube extraction dynamic head-space followed by gas chromatography coupled to mass spectrometry, gives evidence that the lack of heating leads to the preservation of more (semi-)volatile substances like pyridine, which provide cold-brew coffee its unique taste. This pioneering study may give the impetus to investigate further the possibility of cold-brewing coffee, accelerated by more than one order of magnitude, using ultrafast laser systems.

Influence of Pt Alloying on the Fluorescence of Fully Inorganic, Colloidal Gold Nanoclusters.

Noble metal alloy nanoclusters (NCs) are interesting systems as the properties of two or more elements can be combined in one particle, leading to interesting fluorescence phenomena. However, previous studies have been exclusively performed on ligand-capped NCs from wet chemical synthesis. This makes it difficult to differentiate to which extent the fluorescence is affected by ligand-induced effects or the elemental composition of the metal core. In this work, we used laser fragmentation in liquids (LFL) to fabricate colloidal gold-rich bi-metallic AuPt NCs in the absence of organic ligands and demonstrate the suitability of this technique to produce molar fraction series of 1nm alloy NC. We found that photoluminescence of ligand-free NCs is not a phenomenon limited to Au. However, even minute amounts of Pt atoms in the AuPt NCs lead to quenching and red-shift of the fluorescence, which may be attributed to the altered surface charge density.

Nanoparticle Additivation Effects on Laser Powder Bed Fusion of Metals and Polymers-A Theoretical Concept for an Inter-Laboratory Study Design All Along the Process Chain, Including Research Data Management.

In recent years, the application field of laser powder bed fusion of metals and polymers extends through an increasing variability of powder compositions in the market. New powder formulations such as nanoparticle (NP) additivated powder feedstocks are available today. Interestingly, they behave differently along with the entire laser powder bed fusion (PBF-LB) process chain, from flowability over absorbance and microstructure formation to processability and final part properties. Recent studies show that supporting NPs on metal and polymer powder feedstocks enhances processability, avoids crack formation, refines grain size, increases functionality, and improves as-built part properties. Although several inter-laboratory studies (ILSs) on metal and polymer PBF-LB exist, they mainly focus on mechanical properties and primarily ignore nano-additivated feedstocks or standardized assessment of powder feedstock properties. However, those studies must obtain reliable data to validate each property metric's repeatability and reproducibility limits related to the PBF-LB process chain. We herein propose the design of a large-scale ILS to quantify the effect of nanoparticle additivation on powder characteristics, process behavior, microstructure, and part properties in PBF-LB. Besides the work and sample flow to organize the ILS, the test methods to measure the NP-additivated metal and polymer powder feedstock properties and resulting part properties are defined. A research data management (RDM) plan is designed to extract scientific results from the vast amount of material, process, and part data. The RDM focuses not only on the repeatability and reproducibility of a metric but also on the FAIR principle to include findable, accessible, interoperable, and reusable data/meta-data in additive manufacturing. The proposed ILS design gives access to principal component analysis (PCA) to compute the correlations between the material-process-microstructure-part properties.

Impact of Ligands on Structural and Optical Properties of Ag29 Nanoclusters.

A ligand exchange strategy has been employed to understand the role of ligands on the structural and optical properties of atomically precise 29 atom silver nanoclusters (NCs). By ligand optimization, ∼44-fold quantum yield (QY) enhancement of Ag29(BDT)12-x(DHLA)x NCs (x = 1-6) was achieved, where BDT and DHLA refer to 1,3-benzene-dithiol and dihydrolipoic acid, respectively. High-resolution mass spectrometry was used to monitor ligand exchange, and structures of the different NCs were obtained through density functional theory (DFT). The DFT results from Ag29(BDT)11(DHLA) NCs were further experimentally verified through collisional cross-section (CCS) analysis using ion mobility mass spectrometry (IM MS). An excellent match in predicted CCS values and optical properties with the respective experimental data led to a likely structure of Ag29(DHLA)12 NCs consisting of an icosahedral core with an Ag16S24 shell. Combining the experimental observation with DFT structural analysis of a series of atomically precise NCs, Ag29-yAuy(BDT)12-x(DHLA)x (where y, x = 0,0; 0,1; 0,12 and 1,12; respectively), it was found that while the metal core is responsible for the origin of photoluminescence (PL), ligands play vital roles in determining their resultant PLQY.

Photoluminescence of Fully Inorganic Colloidal Gold Nanocluster and Their Manipulation Using Surface Charge Effects.

Fully inorganic, colloidal gold nanoclusters (NCs) constitute a new class of nanomaterials that are clearly distinguishable from their commonly studied metal-organic ligand-capped counterparts. As their synthesis by chemical methods is challenging, details about their optical properties remain widely unknown. In this work, laser fragmentation in liquids is performed to produce fully inorganic and size-controlled colloidal gold NCs with monomodal particle size distributions and an fcc-like structure. Results reveal that these NCs exhibit highly pronounced photoluminescence with quantum yields of 2%. The emission behavior of small (2-2.5 nm) and ultrasmall (<1 nm) NCs is significantly different and dominated by either core- or surface-based emission states. It is further verified that emission intensities are a function of the surface charge density, which is easily controllable by the pH of the surrounding medium. This experimentally observed correlation between surface charge and photoluminescence emission intensity is confirmed by density functional theoretical simulations, demonstrating that fully inorganic NCs provide an appropriate material to bridge the gap between experimental and computational studies of NCs. The presented study deepens the understanding of electronic structures in fully inorganic colloidal gold NCs and how to systematically tune their optical properties via surface charge density and particle size.

In situ speciation and spatial mapping of Zn products during pulsed laser ablation in liquids (PLAL) by combined synchrotron methods.

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.

In situ structural kinetics of picosecond laser-induced heating and fragmentation of colloidal gold spheres.

Fragmentation of colloidal 54 nm gold nanoparticles by picosecond laser pulses is recorded by time-resolved X-ray scattering, giving access to structural dynamics down to a 80 ps resolution. Lattice temperature and energy dissipation have been quantified to verify that the maximum applied fluence of 1800 J m-2 heats up the particles close to boiling. Already within 30 ns, particles with significantly lower particle sizes of 2 to 3 nm are detected, which hints towards an ultrafast process either by a thermal phase explosion or Coulomb instability. An arrested growth is observed on a microsecond time scale resulting in a final particle size of 3-4 nm with high yield. In this context, the fragmentation in a NaCl/NaOH solution seems to limit growth by electrostatic stabilization of fragments, whereas it does not modify the initial product sizes. The laser-induced fragmentation process is identified as a single-step, instantaneous reaction.

Synergism between Specific Halide Anions and pH Effects during Nanosecond Laser Fragmentation of Ligand-Free Gold Nanoparticles.

Gold nanoclusters (AuNCs) with diameters smaller than 3 nm are an emerging field of research because they possess interesting optical properties, such as photoluminescence. However, to date, it is still difficult to distinguish whether these properties originate from the cores of the nanoparticles or from the adsorbates on their surfaces. Hence, there is a high demand for ligand-free, ultra-small particles because they make it possible to study ligand and core effects separately. Pulsed laser fragmentation in liquids (LFL) is a convenient route for the synthesis of ligand-free AuNCs. The influence of physical parameters, such as melting and evaporation, on the LFL process is well understood both theoretically and experimentally. However, the impact of the chemical composition of the medium during LFL, which critically affects the particle formation process, has been less well examined. Therefore, in this work, we elucidate the extent to which the ionic strength, the pH value, and the nature of the halide anion that is present, that is, F-, Cl-, Br-, or I-, influence the particle size distribution of the LFL product and the mean yield of small particles (<3 nm) of the product. We showed that the yield of small particles can be enhanced by the synergism between pH and specific ion effects, which probably is attributable to the adsorption of specific anions. In addition, our findings indicated that anion-based stabilization depends critically on the type of anion. A direct Hofmeister effect was observed for anions in the neutral pH regime, whereas an indirect Hofmeister series was reported in alkaline solution, which probably was due to the more hydrophilic surfaces of the AuNCs that were formed.

Kinetically-controlled laser-synthesis of colloidal high-entropy alloy nanoparticles.

The single-step incorporation of multiple immiscible elements into colloidal high-entropy alloy (HEA) nanoparticles has manifold technological potential, but it continues to be a challenge for state-of-the-art synthesis methods. Hence, the development of a synthesis approach by which the chemical composition and phase of colloidal HEA nanoparticles can be controlled could lead to a new pool of nanoalloys with unparalleled functionalities. Herein, this study reports the single-step synthesis of colloidal CoCrFeMnNi HEA nanoparticles with targeted equimolar stoichiometry and diameters less than 5 nm by liquid-phase, ultrashort-pulsed laser ablation of the consolidated and heat-treated micropowders of the five constituent metals. Further, the scalability of the process with an unprecedented productivity of 3 grams of colloidal HEA nanoparticles per hour is demonstrated. Electrochemical analysis reveals a unique redox behavior of the particles' surfaces in an alkaline environment and a potential for future application as a heterogeneous catalyst for the oxygen evolution reaction.

Inclusion of supported gold nanoparticles into their semiconductor support.

Supported particles are easily accessible as standard materials used in heterogeneous catalysis and photocatalysis. This article addresses our exemplary studies on the integration of supported nanoparticles into their solid support, namely gold nanoparticles into zinc oxide sub-micrometer spheres, by energy controlled pulsed laser melting in a free liquid jet. This one-step, continuous flow-through processing route reverses the educt's structure, converting the ligand-free surface adsorbate into a spherical subsurface solid inclusion within its former support. The results show how a nanoparticulate surface adsorbate can be included in the form of crystalline nanoparticles into the resolidified support matrix, demonstrated by using plasmonic nanoparticles and semiconductor microparticles as reference materials.