Effective size separation of laser-generated, surfactant-free nanoparticles by continuous centrifugation.

High-power, nanosecond, pulsed-laser ablation in liquids enables the continuous synthesis of highly pure colloidal nanoparticles (NPs) at an application-relevant scale. The gained mass-weighted particle size distribution is however often reported to be broad, requiring post treatment like centrifugation to remove undesired particle size fractions. To date, available centrifugation techniques are generally discontinuous, limiting the throughput and hindering economic upscaling. Hence, throughout this paper, a scalable, continuously operating centrifugation of laser-generated platinum NPs in a tubular bowl centrifuge is reported for the first time. To that end, using a 121 W ns-laser, the continuous production of a colloidal suspension of NPs, yet with broad particle size distribution has been employed, yielding productivities of 1-2 g h-1 for gold, silver, and platinum. The power-specific productivities (Au: 18 mg h-1 W-1, Pt: 13 mg h-1 W-1, Ag: 8 mg h-1 W-1, Ni: 6 mg h-1 W-1) are far higher than reported before. Subsequent downstream integration of a continuously operating tubular bowl centrifuge was successfully achieved for Pt NPs allowing the removal of undesired particle size with high throughput. By means of a systematic study of relevant centrifugation parameters involved, effective size optimization and respective size sharpness parameters for a maximum Pt NP diameter of 10 nm are reported. The results of the experimental centrifugation of laser-generated Pt NPs were in excellent agreement with the theoretically calculated cut-off diameter. After centrifugation with optimized parameters (residence time of 5 min; g-force of 38,454 g), the polydispersity indices of the Pt NPs size distributions were reduced by a factor of six, and high monodispersity was observed.

Comprehensive study to design advanced metal-carbide@garaphene and metal-carbide@iron oxide nanoparticles with tunable structure by the laser ablation in liquid.

Core-shell nanoparticles represent a class of materials that exhibit a variety of properties. By rationally tuning the cores and the shells in such nanoparticles (NPs), a range of materials with tailorable properties can be produced which are of interest for a wide variety of applications. Herein, experimental and theoretical approaches have been combined to show the structural transformation of NPs resulting to the formation of either NiFexCy encapsulated in ultra-thin graphene layer (NiFe@UTG) or Ni3C/FexCy@FeOx NPs with the universal one-step pulse laser ablation in liquid (PLAL) method. Analysis suggests that carbon in Ni3C is the source for the carbon shell formation, whereas the final carbon-shell thickness in the NPs originates from the difference between Ni3C and FexCy phases stability at room temperature. The ternary Ni-Fe-C phase diagram calculations reveal the competition between carbon solubility in the studied metals (Ni and Fe) and their tendency toward oxidation as the key properties to produce controlled core-shell NP materials. As an application example, the electrocatalytic hydrogen evolution current on the different NPs is measured. The electrochemical analysis of the NPs reveals that NiFe@UTG has the best performance amongst the NPs in this study in both alkaline and acidic media.

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.

Catalyst Support Effect on the Activity and Durability of Magnetic Nanoparticles: toward Design of Advanced Electrocatalyst for Full Water Splitting.

Earth-abundant element-based inorganic-organic hybrid materials are attractive alternatives for electrocatalyzing energy conversion reactions. Such material structures do not only increase the surface area and stability of metal nanoparticles (NPs) but also modify the electrocatalytic performance. Here, we introduce, for the first time, multiwall carbon nanotubes (MWNTs) functionalized with nitrogen-rich emeraldine salt (ES) (denoted as ES-MWNT) as a promising catalyst support to boost the electrocatalytic activity of magnetic maghemite (γ-Fe2O3) NPs. The latter component has been synthesized by a simple and upscalable one-step pulsed laser ablation method on Ni core forming the core-shell Ni@γ-Fe2O3 NPs. The catalyst (Ni@γ-Fe2O3/ES-MWNT) is formed via self-assembly as strong interaction between ES-MWNT and Ni@γ-Fe2O3 results in NPs' encapsulation in a thin C-N shell. We further show that Ni does not directly function as an active site in the electrocatalyst but it has a crucial role in synthesizing the maghemite shell. The strong interaction between the NPs and the support improves notably the NPs' catalytic activity toward oxygen evolution reaction (OER) in terms of both onset potential and current density, ranking it among the most active catalysts reported so far. Furthermore, this material shows a superior durability to most of the current excellent OER electrocatalysts as the activity, and the structure, remains almost intact after 5000 OER stability cycles. On further characterization, the same trend has been observed for hydrogen evolution reaction, the other half-reaction of water splitting.

Development of A Low-Cost FPGA-Based Measurement System for Real-Time Processing of Acoustic Emission Data: Proof of Concept Using Control of Pulsed Laser Ablation in Liquids.

Today, the demand for continuous monitoring of valuable or safety critical equipment is increasing in many industrial applications due to safety and economical requirements. Therefore, reliable in-situ measurement techniques are required for instance in Structural Health Monitoring (SHM) as well as process monitoring and control. Here, current challenges are related to the processing of sensor data with a high data rate and low latency. In particular, measurement and analyses of Acoustic Emission (AE) are widely used for passive, in-situ inspection. Advantages of AE are related to its sensitivity to different micro-mechanical mechanisms on the material level. However, online processing of AE waveforms is computationally demanding. The related equipment is typically bulky, expensive, and not well suited for permanent installation. The contribution of this paper is the development of a Field Programmable Gate Array (FPGA)-based measurement system using ZedBoard devlopment kit with Zynq-7000 system on chip for embedded implementation of suitable online processing algorithms. This platform comprises a dual-core Advanced Reduced Instruction Set Computer Machine (ARM) architecture running a Linux operating system and FPGA fabric. A FPGA-based hardware implementation of the discrete wavelet transform is realized to accelerate processing the AE measurements. Key features of the system are low cost, small form factor, and low energy consumption, which makes it suitable to serve as field-deployed measurement and control device. For verification of the functionality, a novel automatically realized adjustment of the working distance during pulsed laser ablation in liquids is established as an example. A sample rate of 5 MHz is achieved at 16 bit resolution.

Role of Dissolved and Molecular Oxygen on Cu and PtCu Alloy Particle Structure during Laser Ablation Synthesis in Liquids.

The role of molecular oxygen dissolved in the solvent is often discussed as being an influential factor on particle oxidation during pulsed laser ablation in liquids. However, the formation of the particles during laser synthesis takes place under extreme conditions that enable the decomposition of the liquid medium. Reactive species of the solvent may then affect particle formation due to a chemical reaction in the reactive plasma. Experimental results show a difference between the role of dissolved molecular oxygen and the contribution from the oxygen in water molecules. Using a metallic Cu target in air-saturated water, laser ablation led to 20.5 wt % Cu, 11.5 wt % Cu2 O, and 68 wt % CuO nanoparticles, according to X-ray diffraction results. In contrast to particles obtained in air-saturated water, no CuO was observed in the colloid synthesized in a Schlenk ablation chamber in completely oxygen-free water. Under these conditions, less-oxidized nanoparticles (25 wt % Cu and 75 wt % Cu2 O) were synthesized. The results show that nanoparticle oxidation during laser synthesis is mainly caused by reactive oxygen species from the decomposition of water molecules. However, the addition of molecular oxygen promotes particle oxidation. Storage of the Cu colloid in the presence of dissolved oxygen leads, due to aging, to nanostructures with a higher oxidation state than the freshly prepared colloid. The XRD pattern of the sample prepared in air-saturated acetone showed no crystalline phases, which is possibly due to small crystallites or low particle concentration. Concentration of the particles by centrifugation showed that in the large fraction (>20 nm), even less oxidized nanoparticles (46 wt % Cu and 54 wt % Cu2 O) were present, although the solubility of molecular oxygen is higher in acetone than in water. The nanoparticles in acetone were stable due to a Cu-catalyzed graphite layer formed on their surfaces. The influence of the solvent on alloy synthesis is also crucial. Laser ablation of PtCu3 in air-saturated water led to separated large CuO and Pt-rich spherical nanoparticles, whereas homogeneous PtCu3 alloy nanoparticles were formed in acetone.

Peptide Cross-linkers: Immobilization of Platinum Nanoparticles Highly Dispersed on Graphene Oxide Nanosheets with Enhanced Photocatalytic Activities.

For exerting potential catalytic and photocatalytic activities of metal nanoparticles (MNPs), immobilization of MNPs on a support medium in highly dispersed state is desired. In this Research Article, we demonstrated that surfactant-free platinum nanoparticles (PtNPs) were efficiently immobilized on graphene oxide (GO) nanosheets in a highly dispersed state by utilizing oligopeptide ß-sheets as a cross-linker. The fluorenyl-substituted peptides were designed to form ß-sheets, where metal-binding thiol groups and protonated and positively charged amino groups are integrated on the opposite sides of the surface of a ß-sheet, which efficiently bridge PtNPs and GO nanosheet. In comparison to PtNP/GO composite without the peptide linker, the PtNP/peptide/GO ternary complex exhibited excellent photocatalytic dye degradation activity via electron transfer from GO to PtNP and simultaneous hole transfer from oxidized GO to the dye. Furthermore, the ternary complex showed photoinduced hydrogen evolution upon visible light irradiation using a hole scavenger. This research provides a new methodology for the development of photocatalytic materials by a bottom-up strategy on the basis of self-assembling features of biomolecules.

Laser synthesis, structure and chemical properties of colloidal nickel-molybdenum nanoparticles for the substitution of noble metals in heterogeneous catalysis.

Platinum and iridium are rare and expensive noble metals that are used as catalysts for different sectors including in heterogeneous chemical automotive emission catalysis and electrochemical energy conversion. Nickel and its alloys are promising materials to substitute noble metals. Nickel based materials are cost-effective with good availability and show comparable catalytic performances. The nickel-molybdenum system is a very interesting alternative to platinum in water electrolysis. We produced ligand-free nickel-molybdenum nanoparticles by laser ablation in water and acetone. Our results show that segregated particles were formed in water due to the oxidation of the metals. X-ray diffraction shows a significant change in the lattice parameter due to a diffusion of molybdenum atoms into the nickel lattice with increasing activity in the electrochemical oxygen evolution reaction. Even though the solubility of molecular oxygen in acetone is higher than in water, there were no oxides and a more homogeneous metal distribution in the particles in acetone as seen by TEM-EDX. This showed that dissolved molecular oxygen does not control oxide formation. Overall, the laser ablation of pressed micro particulate mixtures in liquids offers a combinational synthesis approach that allows the screening of alloy nanoparticles for catalytic testing and can convert micro-mixtures into nano-alloys.

In Situ Investigations of Laser-Generated Ligand-Free Platinum Nanoparticles by X-ray Absorption Spectroscopy: How Does the Immediate Environment Influence the Particle Surface?

Pulsed laser ablation in liquid (PLAL) has proven its usefulness as a nanoparticle (NP) synthesis method alternative to traditional chemical reduction methods, where the absence of any molecular ligands or residual reactants makes laser-generated nanoparticles ideal reference materials for charge-transfer experiments. We synthesized additive-free platinum nanoparticles by PLAL and in-situ characterized their interaction with H2O, sodium phosphate buffer, and sodium citrate as well as a TiO2 support by X-ray absorption fine structure (XAFS), i.e., X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Differences in the white-line intensity among the colloidal particles in the three liquids indicate that the respective NP-solvent interaction varies in strength. The ions added ex situ diffuse through the particles' electric double layer and interact electrostatically with the Stern plane. Consequently, these ions weaken the interaction of the functional OH groups that are bound to the partially oxidized platinum surfaces and cause their partial reduction. Comparing XAFS spectra of laser-generated Pt NPs in citrate with wet-chemically synthesized ones (both ligand-covered) indicates different types of Pt-O bonds: a Pt(IV)O2 type in the case of wet-chemical NPs and a Pt(II)O type in the case of laser-generated NPs. A comparison of unsupported laser-generated platinum NPs in H2O with TiO2-supported ones shows no white-line intensity differences and also an identical number of Pt-O bonds in both cases. This suggests that in the deposition process at least part of the double-layer coating stays intact and that the ligand-free Pt particle properties are preserved in the TiO2-supported Pt particles, relevant for heterogeneous catalysis.

Adsorption of colloidal platinum nanoparticles to supports: charge transfer and effects of electrostatic and steric interactions.

Adsorption of colloidal nanoparticles to surfaces and supports is a convenient approach to heterogeneous catalysts, polymer additives, or wastewater treatment. We investigated the adsorption efficiency of laser-generated and initially ligand-free platinum nanoparticles to TiO2 supports as a function of pH, ionic strength, and ligand surface coverage. The nanoparticle adsorption is dominantly controlled by electrostatic interactions: if the pH of the suspension is between the isoelectric point of the nanoparticles and the support, nanoparticles are adsorbed and transfer a net charge to the support. This charge-driven adsorption is not affected by steric repulsion due to various ligands attached to the nanoparticle surface. In addition to electrostatic interactions, colloidal stability given by moderate ionic strengths and pH values above the isoelectric point of nanoparticles are prerequisites for colloidal deposition.