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NiFe catalysts have emerged as promising low-cost alternatives to Ir- or Ru-based anodes for water splitting. Despite their potential, their widespread adoption in commercial alkaline electrolyzers is currently hindered by instability and rapid deactivation under real operating conditions. In this study, we investigate the behavior of NiFe (90/10% at.) thin film (∼35 nm) electrodes fabricated by supersonic cluster beam deposition as electrocatalysts for the oxygen evolution reaction in alkaline media during prolonged electrochemical activity. In particular, we observed that an exfoliation process occurred, leading to the detachment and dissolution of most (∼99%) of the catalyst nanoparticles (NPs) from the electrode surface into the electrolyte. However, upon multiple potential sweeps, a partial NP redeposition occurred. Importantly, we demonstrate the establishment of an equilibrium between the dissolution and readsorption of catalyst NPs from/to the electrode surface, thereby sustaining significant residual catalytic activity.

Here we investigated the dynamics of OER activity of NiFe (90/10) catalysts over 1000 potential sweep cycles as a function of their mass loading. Over twenty different films with mass loading in the 10 ng/cm2-30 mu g/cm2 range were deposited by Supersonic Cluster Beam Deposition (SCBD), allowing to study the progress of OER in sub-monolayer, monolayer and multilayer regimes. Upon prolonged potential sweeps the electrocatalytic performances of multilayers decreased, while those of monolayers were significantly improved. The best balance in terms of catalytic efficiency and stability in working conditions is found for mass loadings corresponding to a NiFe monolayer, corresponding to a mass loading around 1 mu g/cm2 and a thickness of about 3 nm.The Oxygen Evolution Activity of NiFe films with different thickness was monitored over 1000 potential sweep cycles, revealing the optimal mass loading needed to maintain catalytic activity while avoiding excessive material consumption. image

Graphitic carbon nitride (gCN) is a promising n-type semiconductor widely investigated for photo-assisted water splitting, but less studied for the (photo)electrochemical degradation of aqueous organic pollutants. In these fields, attractive perspectives for advancements are offered by a proper engineering of the material properties, e.g., by depositing gCN onto conductive and porous scaffolds, tailoring its nanoscale morphology, and functionalizing it with suitable cocatalysts. The present study reports on a simple and easily controllable synthesis of gCN flakes on Ni foam substrates by electrophoretic deposition (EPD), and on their eventual decoration with Co-based cocatalysts [CoO, CoFe2O4, cobalt phosphate (CoPi)] via radio frequency (RF)-sputtering or electrodeposition. After examining the influence of processing conditions on the material characteristics, the developed systems are comparatively investigated as (photo)anodes for water splitting and photoelectrocatalysts for the degradation of a recalcitrant water pollutant [potassium hydrogen phthalate (KHP)]. The obtained results highlight that while gCN decoration with Co-based cocatalysts boosts water splitting performances, bare gCN as such is more efficient in KHP abatement, due to the occurrence of a different reaction mechanism. The related insights, provided by a multi-technique characterization, may provide valuable guidelines for the implementation of active nanomaterials in environmental remediation and sustainable solar-to-chemical energy conversion.

Introduction: As we approach the post-antibiotic era, the development of innovative antimicrobial strategies that carry out their activities through non-specific mechanisms could limit the onset and spread of drug resistance. In this context, the use of nanogranular coatings of multielement nanoparticles (NPs) conjugated to the surface of implantable biomaterialsmight represent a strategy to reduce the systemicdrawbacks by locally confining the NPs effects against either prokaryotic or eukaryotic cells. Methods: In the present study, two new multielement nanogranular coatings combining Ag and Cu with either Ti or Mg were synthesized by a gas phase physical method and tested against pathogens isolated from periprosthetic joint infections to address their potential antimicrobial value and toxicity in an in vitro experimental setting. Results: Overall, Staphylococcus aureus, Staphylococcus epidermidis and Escherichia coli displayed a significantly decreased adhesion when cultured on Ti-Ag-Cu and Mg-Ag-Cu coatings compared to uncoated controls, regardless of their antibiotic resistance traits. A dissimilar behavior was observed when Pseudomonas aeruginosa was cultured for 30 and 120 minutes upon the surface of Ti-Ag-Cu and Mg-Ag-Cu-coated discs. Biofilm formation was mainly reduced by the active effect of Mg-Ag-Cu compared to Ti-Ag-Cu and, again, coatings had a milder effect on P. aeruginosa, probably due to its exceptional capability of attachment and matrix production. These data were further confirmed by the evaluation of bacterial colonization on nanoparticle-coated discs through confocal microscopy. Finally, to exclude any cytotoxic effects on eukaryotic cells, the biocompatibility of NPs-coated discs was studied. Results demonstrated a viability of 95.8% and 89.4% of cells cultured in the presence of Ti-Ag-Cu and Mg-Ag-Cu discs, respectively, when compared to negative controls. Conclusion: In conclusion, the present study demonstrated the promising antiadhesive fe

Iron-nitrogen-carbon (Fe-N-C) materials emerged as one of the best non-platinum group material (non-PGM) alternatives to Pt/C catalysts for the electrochemical reduction of O2 in fuel cells. Co-doping with a secondary metal center is a possible choice to further enhance the activity toward oxygen reduction reaction (ORR). Here, classical Fe-N-C materials were co-doped with Sn as a secondary metal center. Sn-N-C according to the literature shows excellent activity, in particular in the fuel cell setup; here, the same catalyst shows a non-negligible activity in 0.5 M H2SO4 electrolyte but not as high as expected, meaning the different and uncertain nature of active sites. On the other hand, in mixed Fe, Sn-N-C catalysts, the presence of Sn improves the catalytic activity that is linked to a higher Fe-N4 site density, whereas the possible synergistic interaction of Fe-N4 and Sn-Nx found no confirmation. The presence of Fe-N4 and Sn-Nx was thoroughly determined by extended X-ray absorption fine structure and NO stripping technique; furthermore, besides the typical voltammetric technique, the catalytic activity of Fe-N-C catalyst was determined and also compared with that of the gas diffusion electrode (GDE), which allows a fast and reliable screening for possible implementation in a full cell. This paper therefore explores the effect of Sn on the formation, activity, and selectivity of Fe-N-C catalysts in both acid and alkaline media by tuning the Sn/Fe ratio in the synthetic procedure, with the ratio 1/2 showing the best activity, even higher than that of the iron-only containing sample (jk = 2.11 vs 1.83 A g-1). Pt-free materials are also tested for ORR in GDE setup in both performance and durability tests.

A photocatalytically active bipolar membrane consisting of a CdS photocatalyst and Pd electrocatalyst has been constructed to carry out environmentally relevant oxidation and reduction processes. The ion exchange property of a bipolar membrane (BPM) has allowed us to load the CdS photocatalyst on one side and Pd electrocatalyst on the other side. By inserting the photocatalytic BPM-CdS/Pd membrane between the two compartments of an H-cell, we can separate the reduction and oxidation processes. Following visible light excitation of CdS in the BPM-CdS/Pd membrane, we can induce vectorial electron transfer from CdS to Pd and to an electron acceptor (4-nitrophenol). The holes generated at CdS are scavenged by ethanol or 4-chlorophenol. The photocatalytic reduction rate dependence on the Pd loading in the membrane as well as its effect on modulating the rates of electron and hole transfer processes are discussed. The design of a semiconductor and metal loaded membrane paves the way for improving selectivity and efficiency of photocatalytic processes.

Sacrificial templates present an effective pathway for gaining high-level control over nanoscale reaction products. Atomic layer deposition (ALD) is ideally suited for such approaches due to its ability to replicate the surface topography of a template material through the deposition of an ultrathin conformal layer. Herein, metal nanostructures are demonstrated as sacrificial templates for the formation of architecturally complex and deterministically positioned oxide nanoshells, open-topped nanobowls, vertically standing half-shells, and nanorings. The three-step process sees metal nanocrystals formed in periodic arrays, coated with an ALD-deposited oxide, and hollowed out with a selective etch through nanopores formed in the oxide shell. The procedure is further augmented through the use of a directional ion beam that is used to sculpt the oxide shells into bowl- and ring-like configurations. The functionality of the so-formed materials is demonstrated through their use as substrate-confined nanoreactors able to promote the growth and confinement of nanomaterials. Taken together, the work expands the design space for substrate-based nanomaterials, creates a platform for advancing functional surfaces and devices and, from a broader perspective, advances the use of ALD in forming complex nanomaterials.The nanofabrication of periodic arrays of structurally complex oxide nanoshells is demonstrated. The so-formed structures are demonstrated as substrate-confined nanoreactors able to synthesize nanomaterials within their confines.

Following recent literature work, an interesting result on hydrogen sorption by Ag–Rh clusters was reported which do not follow the common understanding of hydrogen absorption in bulk alloys. Thus, nanostructured Ag–Rh films with a composition of 75% Ag–25% Rh were grown by supersonic cluster beam deposition onto microbalance quartz crystals in order to measure hydrogen absorption. The films were exposed to H2 gas to study hydrogen absorption at different partial pressure. The Ag–Rh films were then characterized by XPS and AFM. The Ag/Rh atomic ratio was found to be 75/25 by XPS. Surface roughness was determined by AFM to be 3 nm RMS in all the films. In disagreement with the quoted literature report, no hydrogen absorption was observed in our Ag–Rh films up to 5.3×103Pa of hydrogen pressure. The response of the balance was checked and validated by measuring hydrogen absorption on 10 and 100 nm Pd films. The hydrogen absorption by Pd yielded an atomic H/Pd ratio of ∼0.65 in agreement with our prior measurements.

In multicomponent thin films, properties and functionalities related to post-deposition annealing treatments, such as thermal stability, optical absorption and surface morphology are typically ra-tionalized, neglecting the role of the substrate. Here, we show the role of the substrate in deter-mining the temperature dependent behaviour of a paradigmatic two-component nanogranular thin film (Ag/TiO2) deposited by gas phase supersonic cluster beam deposition (SCBD) on silica and sapphire. Up to 600 °C, no TiO2 grain growth nor crystallization is observed, likely inhibited by the Zener pinning pressure exerted by the Ag nanoparticles on the TiO2 grain boundaries. Above 600 °C, grain coalescence, formation of anatase and rutile phases and drastic modification of the optical absorption are observed. However, the two substrates steer the evolution of the film morphology and optical properties in two different directions. On silica, Ag is still present as NPs distributed into the TiO2 matrix, while on sapphire, hundreds of nm wide Ag aggregates appear on the film surface. Moreover, the silica-deposited film shows a broad absorption band in the visi-ble range while the sapphire-deposited film becomes almost transparent for wavelengths above 380 nm. We discuss this result in terms of substrate differences in thermal conductivity, thermal expansion coefficient and Ag diffusivity. The study of the substrate role during annealing is possi-ble since SCBD allows the synthesis of the same film independently of the substrate, and suggests new perspectives on the thermodynamics and physical exchanges between thin films and their substrates during heat treatments.

A one-dimensional (1D) mechanical model for nanogranular films, based on a structural interface, is presented. The analytical dispersion relation for the frequency and lifetimes of the acoustics breathing modes is obtained in terms of the interface layer thickness and porosity. The model is successfully benchmarked both against three-dimensional finite element method simulations and experimental photoacoustic data on a paradigmatic system available from the literature. A simpler 1D model, based on an homogenized interface, is also presented and its limitations and pitfalls discussed at the light of the more sophisticated pillar model. The pillar model captures the relevant physics responsible for acoustic dissipation at a disordered interface. Furthermore, the present findings furnish to the experimentalist an easy-to-adopt, benchmarked analytical tool to extract the interface layer physical parameters upon fitting of the acoustic data. The model is scale invariant and may be deployed, other than the case of granular materials, where a patched interface is involved.

A photocatalytic system for the degradation of aqueous organic pollutants under visible light irradiation is obtained by an innovative approach based on ceria/platinum (Pt) hybrid nanoclusters on cellulose acetate fibrous membranes. The catalytic materials are fabricated by supersonic beam deposition of Pt nanoclusters directly on the surface of electrospun cellulose acetate fibrous mats, pre-loaded with a cerium salt precursor that is transformed into ceria nanoparticles directly in the solid mats by a simple thermal treatment. The presence of Pt enhances the oxygen vacancies on the surface of the formed ceria nanoparticles and reduces their band gap, resulting in a significant improvement of the photocatalytic performance of the composite mats under visible light irradiation. Upon the appropriate pretreatment and visible light irradiation, we prove that the most efficient mats, with both ceria nanoparticles and Pt nanoclusters, present a degradation efficiency of methylene blue of 70% and a photodegradation rate improved by about five times compared to the ceria loaded samples, without Pt. The present results bring a significant improvement of the photocatalytic performance of polymeric nanocomposite fibrous systems under visible light irradiation, for efficient wastewater treatment applications.

Nanostructured materials may provide a route to overcome the electrode-limiting performance in water splitting, the oxygen evolution reaction (OER), within the framework of low-cost catalysts search. However, for alloyed NiFe nanostructures, the relationship among the OER efficiency and the electrode physical characteristics (morphology, porosity, size, thickness, or mass loading) is largely unknown. This work introduces a new type of alloyed NiFe (90/10% at) nanogranular electrodes obtained by supersonic cluster beam deposition and investigates the dependence of their catalytic activity toward the OER on the film morphological and stoichiometric properties. The synthesized alloyed NiFe nanoparticles with 0.3-3.8 nm size assemble from the gas phase to form ultrathin film electrodes with thickness in the 15-88 nm range, corresponding to 5-30 mu g/cm2 mass loading. The fitting of the optical spectroscopic data by an effective medium approximation model suggests that, independent of the thickness, the films have a 20% porosity and are completely hydroxydated. The resulting catalytic efficiency is independent on the film thickness, while the turnover frequency decreases with increasing electrode loading. These data suggest that an excess of catalyst mass with respect to the OER active sites is deposited in the case of thicker electrodes and sets the 15 nm film as an upper loading limit to maximize the electrocatalyst efficiency. This study represents a crucial step toward thickness optimization of NiFe electrodes to fabricate low-cost OER catalysts.

Counteracting the spreading of multi-drug-resistant pathogens, taking place through surface-mediated cross-contamination, is amongst the higher priorities in public health policies. For these reason an appropriate design of antimicrobial nanostructured coatings may allow to exploit dierent antimicrobial mechanisms pathways, to be specifically activated by tailoring the coatings composition and morphology. Furthermore, their mechanical properties are of the utmost importance in view of the antimicrobial surface durability. Indeed, the coating properties might be tuned dierently according to the specific synthesis method. The present review focuses on nanoparticle based bactericidal coatings obtained via magneton-spattering and supersonic cluster beam deposition. The bacteria–NP interaction mechanisms are first reviewed, thus making clear the requirements that a nanoparticle-based film should meet in order to serve as a bactericidal coating. Paradigmatic examples of coatings, obtained by magnetron sputtering and supersonic cluster beam deposition, are discussed. The emphasis is on widening the bactericidal spectrum so as to be eective both against gram-positive and gram-negative bacteria, while ensuring a good adhesion to a variety of substrates and mechanical durability. It is discussed how this goal may be achieved combining dierent elements into the coating.

Bactericidal nanoparticle coatings are very promising for hindering the indirect transmission of pathogens through cross-contaminated surfaces. The challenge, limiting their employment in nosocomial environments, is the ability of tailoring the coating's physicochemical properties, namely, composition, cytotoxicity, bactericidal spectrum, adhesion to the substrate, and consequent nanoparticles release into the environment. We have engineered a new family of nanoparticle-based bactericidal coatings comprising Ag, Cu, and Mg and synthesized by a green gas-phase technique. These coatings present wide-spectrum bactericidal activity on both Gram-positive and Gram-negative reference strains and tunable physicochemical properties of relevance in view of their "on-field" deployment. The link between material and functional properties is rationalized based on a multidisciplinary and multitechnique approach. Our results pave the way for engineering biofunctional, fully tunable nanoparticle coatings, exploiting an arbitrarily wide number of elements in a straightforward, eco-friendly, high-throughput, one-step process.

Nanoporous ultrathin films, constituted by a slab less than 100 nm thick and a certain void volume fraction provided by nanopores, are emerging as a new class of systems with a wide range of possible applications, including electrochemistry, energy storage, gas sensing and supercapacitors. The film porosity and morphology strongly affect nanoporous films mechanical properties, the knowledge of which is fundamental for designing films for specific applications. To unveil the relationships among the morphology, structure and mechanical response, a comprehensive and nondestructive investigation of a model system was sought. In this review, we examined the paradigmatic case of a nanoporous, granular, metallic ultrathin film with comprehensive bottom-up and top-down approaches, both experimentals and theoreticals. The granular film was made of Ag nanoparticles deposited by gas-phase synthesis, thus providing a solvent-free and ultrapure nanoporous system at room temperature. The results, bearing generality beyond the specific model system, are discussed for several applications specific to the morphological and mechanical properties of the investigated films, including bendable electronics, membrane separation and nanofluidic sensing.

The ongoing miniaturization of electronic devices has boosted the development of new post-silicon two-dimensional (2D) semiconductors, such as transition metal dichalcogenides, one of the most prominent materials being molybdenum disulfide (MoS2). A major obstacle for the industrial production of MoS2-based devices lies in the growth techniques. These must ensure the reliable fabrication of MoS2 with tailored 2D properties to allow for the typical direct bandgap of 1.9 eV, while maintaining large-area growth and device compatibility. In this work, we used a versatile and industrially scalable MoS2 growth method based on ionized jet deposition and annealing at 250 °C, through which a 3D stable and scalable material exhibiting excellent electronic and optical properties of 2D MoS2 is synthesized. The thickness-related limit, i.e., the desired optical and electronic properties being limited to 2D single/few-layered MoS2, was overcome in the thin film through the formation of encapsulated highly crystalline 2D MoS2 nanosheets exhibiting a bandgap of 1.9 eV and sharp optical emission. The newly synthesized 2D-in-3D MoS2 structure will facilitate device compatibility of 2D materials and confer superior optoelectronic device function.