A key enabling step in leveraging the properties of nanoparticles (NPs) is to explore new, simple, controllable, and scalable nanotechnologies for their syntheses. Among "wet" methods, cathodic corrosion has been used to synthesize catalytic aggregates with some control over their size and preferential faceting. Here, we report on a modification of the cathodic corrosion method for producing a range of nonaggregated nanocrystals (Pt, Pd, Au, Ag, Cu, Rh, Ir, and Ni) and nanoalloys (Pt₅₀Au₅₀, Pd₅₀Au₅₀, and Ag_xAu_100-x) with potential for scaling up the production rate. The method employs poly(vinylpyrrolidone) (PVP) as a stabilizer in an electrolyte solution containing nonreducible cations (Na⁺, Ca²⁺), and cathodic corrosion of the corresponding wires takes place in the electrolyte under ultrasonication. The ultrasonication not only promotes particle-PVP interactions (enhancing NP dispersion and diluting locally high NP concentration) but also increases the production rate by a factor of ca. 5. Further increase in the production rate can be achieved through parallelization of electrodes to construct comb electrodes. With respect to applications, carbon-supported Pt NPs prepared by the new method exhibit catalytic activity and durability for methanol oxidation comparable or better than the commercial benchmark catalyst. A variety of Ag_xAu_100-x nanoalloys are characterized by ultraviolet-visible absorption spectroscopy and high-resolution transmission electron microscopy. The protocol for NP synthesis by cathodic corrosion should be a step toward its further use in academic research as well as in its practical upscaling.

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Using the magnetocaloric effect in nanoparticles holds great potential for efficient refrigeration and energy conversion. The most promising candidate materials for tailoring the Curie temperature to room temperature are rare-earth-based magnetic nanoalloys. However, only few high-nuclearity lanthanide/transition-metal nanoalloys have been produced so far. Here we report, for the first time, the observation of magnetic response in spark-produced LaFeSi nanoalloys. The results suggest that these nanoalloys can be used to exploit the magnetocaloric effect near room temperature; such a finding can lead to the creation of unique multicomponent materials for energy conversion, thus helping toward the realization of a sustainable energy economy.

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The increasing need for engineered alloy nanoparticles (NPs) in diverse fields has spurred efforts to explore efficient/green synthesis methods. In this respect, spark ablation provides a scalable and viable way for producing widely different types of mixed NPs. Most importantly, implementation of the spark has the great advantage to combine a wider range of materials, thereby allowing the synthesis of mixed NPs with virtually unlimited combinations. Here we show that polarity reversal of spark discharges between two electrodes consisting of different materials enables synthesis of alloy NPs, while having a good potential to control the broadness of their composition distribution. A model developed in this work provides a tool for tuning the ablation ratio between the electrodes by adjusting the electric characteristics of the spark circuit. The ablation ratio is equal to the mean composition of the resulting NPs. The model predictions are in accordance with measurements obtained here and in earlier works. The unique way of producing alloy NPs by spark ablation shown in this work becomes especially useful when the starting electrode materials are immiscible at macroscopic scale.

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High-yield and continuous synthesis of ultrapure inorganic nanoparticles (NPs) of well-defined size and composition has invariably been one of the major challenges in nanotechnology. Employing green techniques that avoid the use of poisonous and expensive chemicals has been realized as a necessity for manufacturing NPs on an industrial scale. In this communication, we show that a newly developed high-frequency spark (HFS) quenched by a high-purity gas yields a series of monometallic and bimetallic NPs in large quantities, with well-defined (primary) particle size (sub-10 nm) and chemical composition. The mass production rate is linearly dependent on the operating frequency, and can reach up to 1 g h−1, providing a universal and facile technology for producing multicomponent hybrid NPs. Considering also that the methodology requires neither any specialized machinery, nor any chemical reagents, product purification, or any further waste processing, it provides a green, sustainable and versatile platform for manufacturing key building blocks toward industrial scale production.@en

A major challenge in nanotechnology is that of determining how to introduce green and sustainable principles when assembling individual nanoscale elements to create working devices. For instance, textile nanofinishing is restricted by the many constraints of traditional pad-dry-cure processes, such as the use of costly chemical precursors to produce nanoparticles (NPs), the high liquid and energy consumption, the production of harmful liquid wastes, and multistep batch operations. By integrating low-cost, scalable, and environmentally benign aerosol processes of the type proposed here into textile nanofinishing, these constraints can be circumvented while leading to a new class of fabrics. The proposed one-step textile nanofinishing process relies on the diffusional deposition of aerosol NPs onto textile fibers. As proof of this concept, we deposit Ag NPs onto a range of textiles and assess their antimicrobial properties for two strains of bacteria (i.e., Staphylococcus aureus and Klebsiella pneumoniae). The measurements show that the logarithmic reduction in bacterial count can get as high as ca. 5.5 (corresponding to a reduction efficiency of 99.96%) when the Ag loading is 1 order of magnitude less (10 ppm; i.e., 10 mg Ag NPs per kg of textile) than that of textiles treated by traditional wet-routes. The antimicrobial activity does not increase in proportion to the Ag content above 10 ppm as a consequence of a "saturation" effect. Such low NP loadings on antimicrobial textiles minimizes the risk to human health (during textile use) and to the ecosystem (after textile disposal), as well as it reduces potential changes in color and texture of the resulting textile products. After three washes, the release of Ag is in the order of 1 wt %, which is comparable to textiles nanofinished with wet routes using binders. Interestingly, the washed textiles exhibit almost no reduction in antimicrobial activity, much as those of as-deposited samples. Considering that a realm of functional textiles can be nanofinished by aerosol NP deposition, our results demonstrate that the proposed approach, which is universal and sustainable, can potentially lead to a wide number of applications.

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Among the numerous point vapor sources, microsecond-pulsed spark ablation at atmospheric pressure is a versatile and environmentally friendly method for producing ultrapure inorganic nanoparticles ranging from singlets having sizes smaller than 1 nm to larger agglomerated structures. Due to its fast quenching and extremely high supersaturation, coagulational growth already begins at the atomic scale at room temperature. On the basis of this knowledge, we develop a simple semiempirical yet versatile model for predicting the size distribution of singlet particles as a function of the process conditions. The model assumes that a plume of a turbulent aerosol flow flares out from a concentrated point source, eventually reaching the walls of the confinement where a fraction of the particles is deposited. Despite the complexity of the entire process, the concentration and size evolution of particles can be adequately described by a first-order differential equation accounting for coagulation, turbulent dilution, and diffusional deposition to the walls. The model provides a simple and practical tool that can generally be used to design and control point vapor source reactors for the synthesis of singlets with tunable sizes starting from that of single atoms.@en

A major challenge in nanotechnology is that of determining how to introduce green principles when assembling individual nanoscale elements to create multifunctional working devices. This dissertation focuses on fundamentals (Part A), scaling-up (Part B) and application (Part C) of nanoparticles with sub-10 nm in size produced by ambient spark ablation, which is a scalable and environmentally benign process, providing great versatility in producing inorganic nanoparticles consisting of a wide variety of conducting or semiconducting materials with virtually unlimited mixing possibilities. In Part A, a new ‘singlet’ concept has been introduced, which rules out the pseudo-paradigm: continuous gas-phase synthesis of nanoparticles is associated with rapid agglomeration. Subsequently, a general approach has been developed to describe the size distributions of singlet particles as a function of the process conditions. In Part B, a newly developed high-frequency spark yields a series of monometallic and bimetallic nanoparticles, sub-10 nm (primary) particles and well-defined chemical composition, providing a green and versatile platform for manufacturing key building blocks toward industrial scale. To improve the uniformity of nanoparticles, inhibition of ‘splashing’ particles (larger than 100 nm) has been successfully achieved by using an external magnetic field within the inter-electrode gap. The resulting Lorenz force deflects the continuous glowing current, onto which sparks are superimposed, thereby avoiding the sparks to strike the same point of electrode surface. To explore internal nanoparticle mixing, a model developed here links the composition of nanoparticles to spark oscillations. In Part C, by integrating gas-phase nanoparticle syntheses into textile nanofinishing, a number of constraints encountered in traditional wet-finishing processes, can be circumvented while creating a new class of fabrics. As proof of this concept, Ag nanoparticles are deposited onto a range of textiles, imparting high antimicrobial activities and exhibiting good washing durability. Accounting for the green, scalability and versatility of the technique used here as well as its compatibility with the existing fabrication processes, the generated nanoparticles bear a great potential for creating multifunctional working devices. @en