Metal nitride and metal oxide nanoparticles (NPs) provide key material components for a number of applications due to their unique properties. Here we demonstrate that spark ablation of metallic electrodes, quenched with a pure N₂ flow at atmospheric pressure, can be used as a reactive generator to synthesize metal nitride, metal oxide or pure metallic NPs depending on the material. The composition of the synthesized NPs was determined through their crystal structure using X-ray diffraction and transmission electron microscopy (TEM). Our results show that the composition of the resulting NPs strongly depends on the electrode material: Ti and Al form mixtures of metal nitride and oxide NPs, whereas Mg and Pd produce respectively only oxide and pure metallic NPs. Repeated XRD measurements of the samples after exposing them to ambient air over periods of several months showed that the stability of TiN was higher compared to that of the AIN NPs, with the first being converted to TiN_yO_x and the latter to γ-Al₂O₃ after 9 months.

The electrochemical conversion of CO₂ into acetaldehyde offers a sustainable and green alternative to the Wacker process. However, current electrocatalysts cannot effectively compete with heterogeneous processes owing to their limited selectivity towards acetaldehyde, resulting in low energy efficiencies. Here we report a theory-guided synthesis of a series of Cu-cluster catalysts (~1.6 nm) immobilized on various heteroatom-doped carbonaceous supports, produced via spark ablation of Cu electrodes (2.6 μg h⁻¹ production rate, 6 Wh energy consumption). These catalysts achieve acetaldehyde selectivity of up to 92% at only 600 mV from the equilibrium potential. In addition, the catalysts exhibit exceptional catalytic stability during a rigorous 30 h stress test involving three repeated start–stop cycles. In situ X-ray absorption spectroscopy reveals that the initial oxide clusters were completely reduced under cathodic potential and maintained their metallic nature even after exposure to air, explaining the stable performance of the catalyst. First-principles simulations further elucidate a possible mechanism of CO₂ conversion to acetaldehyde. (Figure presented.)

This article describes a single-step method for synthesizing nanostructured materials using evaporation-condensation synthesis and inertial impaction of aerosol nanoparticles. The as-deposited films exhibit anisotropic vertical and horizontal sintering of their palladium nanoparticle building blocks, yielding vertical structures. The electrical conductivity of the films is stable and highly sensitive to the presence of hydrogen in the overlaying gas, at concentrations that range from a few hundreds parts per million to a few percent.

Spark ablation is a highly effective and versatile method for producing nanoparticles from bulk conductive electrode materials. For a number of applications, however, the production throughput of the process needs to be increased with respect to the current state of the art. Here we show that this can be achieved by decreasing the diameter of the employed bulk-material electrodes from ca. 12 to 0.15 mm, corroborating previous observations, and demonstrate that the throughput is associated with the ablation efficiency (i.e., the energy spent to produce nanoparticles per total input energy) that respectively increases by a factor of 10. It is also shown that the commonly used theory for predicting the mass of nanoparticles produced by spark ablation cannot capture this effect, and thus we extend it to account for heat losses that affect the process when electrode diameter reduces below ca. 2 mm. Through this exercise we also show that reduced heat losses associated with thinner electrodes provide an effective recipe to increase the ablation efficiency, also referred as the nanoparticle production yield. The new extended theory for estimating spark ablation nanoparticle mass production throughput is also accompanied by an empirical equation predicting its dependence on electrode diameter.

The stability of nanoparticle (NP) production by atmospheric-pressure spark ablation was studied and found to depend on the composition of the electrodes and the carrier gas (here N₂ or Ar). For materials that do not react with N₂, such as Pd and Ni, NP production was rather stable regardless of the carrier gas employed. In contrast, for materials that can easily produce nitride species (e.g., Al and Mg), both the concentration and size of the resulting NPs exhibited noticeable fluctuations, when ablating them in N₂, which are more pronounced when the electrical energy input to the system is low. The variation in concentration and particle size is attributed to the formation of a metal-nitride region on the face of the electrodes where the sparks hit, as a result of its reaction with the carrier gas, altering the electrical and thermal conductivity, and consequently the ablatability of the electrode at that region. This explanation was corroborated by offline analysis of the face surface of the electrodes, showing two chemically distinct regions: one with high content of N and one without. In addition, the concentration of the Al and Mg NPs produced in N₂ decreased gradually over time until it reached a plateau after several hours. When using Ar, the fluctuation and decreasing trend in NP production, and consequently the formation of nitride compounds on the face surface of the electrodes, were negligible, providing an effective solution for stable ablation of materials that can easily react with N₂.

Photocatalyst synthesis typically involves multiple steps, expensive precursors, and solvents. In contrast, spark ablation offers a simple process of electrical discharges in a gap between two electrodes made from a desirable material. This enables a precursor- and waste-free generation of pure metal oxide nanoparticles or mixtures of various compositions. This study presents a two-step method for the production of photocatalytic filters with deposited airborne MnO_x, TiO₂, and ZnO nanoparticles using spark ablation and calcination processes. The resulting MnO_x and TiO₂ filters demonstrated almost twice the activity with outstanding performance stability, as compared to sol-gel MnO₂ and commercial TiO₂. The introduced method is not only simple, precursor- and waste-free, and leads to superior performance for the case studied, but it also has future potential due to its versatility. It can easily produce mixed and doped materials with further improved properties, making it an interesting avenue for future research.

Nanoparticles (NPs) mixed at the atomic scale have been synthesized by atmospheric-pressure spark ablation using pairs of Pd and Hf electrodes. Gravimetric analysis of the electrodes showed that the fraction of each material in the resulting mixed NPs can be varied from ca. 15-85 at% to 85-15 at% by employing different combinations of electrode polarities and thicknesses. These results were also qualitatively corroborated by microscopy and elemental analysis of the produced NPs. When using pairs of electrodes having the same diameter, the material from the one at negative polarity was represented at a substantially higher fraction in the mixed NPs regardless of whether a pair of thin or thick electrodes were employed. This can be attributed to the higher ablation rate of the electrodes at the negative polarity, as already known from earlier experiments. When using electrodes of different diameters, the fraction of the element from the thinner electrode was always higher. This is because thinner electrodes are ablated more effectively due to, at least in part, the increased importance of the associated heat losses compared to its thicker counterpart. In those cases, the polarity of the electrodes had a significantly smaller effect. Overall, our results demonstrate, for the first time, that spark ablation can be used to control atomic scale mixing and thus produce alloyed NPs with compositions that can be tuned to a good extent by simply using different combinations of electrode diameters and polarities. This expands the capabilities of the technique for producing mixed nanoparticle building blocks of well-defined composition that are highly desired for a wide range of applications.

Silver oxide cluster cations (AgnOm+) can readily be produced by a number of methods including atmospheric-pressure spark ablation of pure silver electrodes when trace amounts of oxygen are present in the carrier gas. Here we determine the equilibrium geometries of AgnOm+ clusters (n = 1-4; m = 1-5) using accurate coupled cluster with singles and doubles (CCSD) method, while the stabilization energies are calculated with additional perturbative triples correction (CCSD(T)). Although a number of stable states have been identified, our results show that the AgnOm+ clusters with m = 1 are more stable than those with m ≥ 2 due to the absence of the terminally attached O2 molecule, corroborating recent observations by mass spectrometry. Using the computed structures, we calculate the electrical mobilities of the AgnOm+ clusters and label the values on a respective experimentally determined spectrum in an attempt to better interpret the occurrence of the peaks and troughs in the measurements.

Advances in semiconductor device manufacturing technologies are enabled by the development and application of novel materials. Especially one class of materials, nanoporous films, became building blocks for a broad range of applications, such as gas sensors and interconnects. Therefore, a versatile fabrication technology is needed to integrate these films and meet the trend towards device miniaturization and high integration density. In this study, we developed a novel method to pattern nanoporous thin films with high flexibility in material selection. Herein, Au and ZnO nanoparticles were synthesized by spark ablation and printed on a Ti/TiO2 adhesion layer, which was exposed by a lithographic stencil mask. Subsequently, the photoresist was stripped by a cost-efficient lift-off process. Nanoporous patterned features were thus obtained and the finest feature has a gap width of 0.6 μ fm and a line width of 2 μ fm. Using SEM and profilometers to investigate the structure of the films, it was demonstrated that the lift-off process had a minor impact on the microstructure and thickness. The samples presented a rough surface and high porosity, indicating a large surface-to-volume ratio. This is supported by the measured conductivity of Au nanoporous film, which is 12% of the value for bulk Au. As lithographic stencil printing is compatible with conventional lithographic pattering, this method enables further application on mass production of various nanoporous film-based devices in the future.

A method is presented to directly measure the mass output of an impaction printer coupled with a spark ablation generator. It is based on a quartz crystal microbalance and shown to be reliable in quantifying mass deposition rate. Here, the method is demonstrated with an Au nanoparticle aerosol synthesized under several spark ablation and deposition settings. Changes in the deposition rate in response to changed synthesis conditions follow the spark ablation models on generation rate made in previous studies, validating this novel measurement method. In combination with the volume of a deposit, a good estimate of the film porosity can be made. The Au nanoparticle films synthesized here have a low porosity of 0.18 due to extensive restructuring and compaction on impact with the substrate. The porosity is found to be insensitive to deposition settings and is constant throughout the film. The simplicity and low cost of a quartz crystal microbalance setup make this an accessible method to determine porosity in porous thin films.

The potential of using atmospheric-pressure spark ablation for production of atomic clusters has been shown in the recent past. In this study we used this method to produce atomic clusters in Argon and investigated their chemical composition with an atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF-MS). Both anionic and cationic silver and gold clusters were generated and characterised. The carrier gas was used directly from the gas cylinder without the application of any additional gas purification. As a result, the carrier gas stream contained trace impurities of N₂, O₂, and H₂O, as well as radicals such as O, OH, and H and their ionized forms resulting from the plasma created by the sparks. The experimental results show that different reactivities towards oxygen and water traces can be observed depending on the number of metal atoms in the clusters, their polarity, as well as their compositions; e.g., Au_n⁻ shows less reactive behaviour towards oxygen and hydrogen compared to Ag_n⁻. The results also show that certain cluster types can be generated at large enough quantities by atmospheric-pressure spark ablation, which considering the low installation and operating cost of the technique can pave the way towards its exploitation for numerous technological applications.

La(OH)₃ metal engineered nanoparticles (MENPs) are efficient phosphate binders; however, complex synthesis procedures and purity as well as agglomeration issues impede their development and practical applications. Herein, a green and a one-step method in combination with the spark ablation aerosol technology and electrospinning is proposed for the synthesis of La(OH)₃ MENPs; further, their application as phosphate binders are elucidated as a proof the concept. Material characterization results confirm the successful synthesis of ultrapure La(OH)₃ MENPs, which has not been achieved before via an environmentally friendly one-step procedure. Small angle X-ray scattering and X-ray photoelectron spectroscopy etching results show that La(OH)₃ MENPs loading on the electrospun nanofibers are uniform in both two and three dimensions. The comparative tests revealed a high phosphate adsorption capacity (110.8 mg P/g La) and indicted that the La(OH)₃ MENPs perform well; this was observed even under the interference of coexisting ions (Cl⁻, SO₄ ²⁻, NO₃ ⁻, and F⁻) at different pH values. After three cycles of solution-shaking treatment, the release of La(OH)₃ was less than 1 wt% (0.5 wt%), which was acceptable for an adsorbent. These results indicate that the La(OH)₃ MENP-loaded nanofibers are practical phosphate binders due to the simple production methods, low manufacturing cost, and impressive capacity. The proposed method significantly shortens the loading process and is a promising alternative for not only the synthesis of the adsorbent, but also for other engineering materials where loading is needed.

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.

The use of disc diffusion susceptibility tests to determine the antibacterial activity of engineered nanoparticles (ENPs) is questionable because their low diffusivity practically prevents them from penetrating through the culture media. In this study, we investigate the ability of such a test, namely the Kirby-Bauer disc diffusion test, to determine the antimicrobial activity of Au and Ag ENPs having diameters from 10 to 40 nm on Escherichia coli cultures. As anticipated, the tests did not show any antibacterial effects of Au nanoparticles (NPs) as a result of their negligible diffusivity through the culture media. Ag NPs on the other hand exhibited a strong antimicrobial activity that was independent of their size. Considering that Ag, in contrast to Au, dissolves upon oxidation and dilution in aqueous solutions, the apparent antibacterial behavior of Ag NPs is attributed to the ions they release. The Kirby-Bauer method, and other similar tests, can therefore be employed to probe the antimicrobial activity of ENPs related to their ability to release ions rather than to their unique size-dependent properties. [Figure not available: see fulltext.].

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.

The detection efficiency of Condensation Particle Counters (CPCs) reduces drastically as particle size becomes smaller than 2 nm. Increasing the supersaturation in order to enhance the detection efficiency, has limited applicability because the onset supersaturation value of droplet formation by homogeneous nucleation is very close to the heterogeneous onset supersaturation for sub-2 nm particles. In this work we introduce a new method for increasing the detection efficiency of CPCs for sub-2 nm particles, which relies mainly on controlling the spatial distribution of the supersaturation profile by simply modifying the operating temperatures of the CPC. We evaluated the new method by generating monodisperse particles in the size range of 0.98–4.50 nm and used them to characterize a TSI 3025 CPC. We achieved significant increase of the detection efficiency for sub-2 nm particles. Furthermore, we calculated the supersaturation field developed in the condenser tube with a finite element model and used it to determine the detection efficiency according to heterogeneous nucleation theory. These calculations reveal that the observed increase of the detection efficiency can be explained by the manipulation of the spatial distribution of the supersaturation field. The method introduced here can greatly improve the detection efficiency of CPCs and in the meantime further extend their use for particle sizing purposes in the sub-2-nm range.

The conversion of light to electrical and chemical energy has the potential to provide meaningful advances to many aspects of daily life, including the production of energy, water purification, and optical sensing. Recently, plasmonic nanoparticles (PNPs) have been increasingly used in artificial photosynthesis (e.g., water splitting) devices in order to extend the visible light utilization of semiconductors to light energies below their band gap. These nanoparticles absorb light and produce hot electrons and holes that can drive artificial photosynthesis reactions. For n-type semiconductor photoanodes decorated with PNPs, hot charge carriers are separated by a process called hot electron injection (HEI), where hot electrons with sufficient energy are transferred to the conduction band of the semiconductor. An important parameter that affects the HEI efficiency is the nanoparticle composition, since the hot electron energy is sensitive to the electronic band structure of the metal. Alloy PNPs are of particular importance for semiconductor/PNPs composites, because by changing the alloy composition their absorption spectra can be tuned to accurately extend the light absorption of the semiconductor. This work experimentally compares the HEI efficiency from Ag, Au, and Ag/Au alloy nanoparticles to TiO₂ photoanodes for the photoproduction of hydrogen. Alloy PNPs not only exhibit tunable absorption but can also improve the stability and electronic and catalytic properties of the pure metal PNPs. In this work, we find that the Ag/Au alloy PNPs extend the stability of Ag in water to larger applied potentials while, at the same time, increasing the interband threshold energy of Au. This increasing of the interband energy of Au suppresses the visible-light-induced interband excitations, favoring intraband excitations that result in higher hot electron energies and HEI efficiencies.

Recent advanced in the fields of nanotechnology and atmospheric sciences underline the increasing need for sizing sub-10-nm aerosol particles in a simple yet efficient way. In this article, we develop, experimentally test and model the performance of a High-Pass Electrical Mobility Filter (HP-EMF) that can be used for sizing nanoparticles suspended in gaseous media. Experimental measurements of the penetration of nanoparticles having diameters down to ca 1nm through the HP-EMF are compared with predictions by an analytic, a semi-empirical and a numerical model. The results show that the HPEMF effectively filters nanoparticles below a threshold diameter with an extremely high level of sizing performance, while it is easier to use compared to existing nanoparticle sizing techniques through design simplifications. What is more, the HP-EMF is an inexpensive and compact tool, making it an enabling technology for a variety of applications ranging from nanomaterial synthesis to distributed monitoring of atmospheric nanoparticles.