Insights into the Photoelectrocatalytic Behavior of gCN-Based Anode Materials Supported on Ni Foams

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

Analytical model of the acoustic response of nanogranular films adhering on a substrate

A 1D mechanical model for nanogranular films, based on a structural interface, is here 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 3D 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 Bipolar CdS/Pd Photocatalytic Membrane for Selective Segregation of Reduction and Oxidation Processes

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

Pilot-Symbols Aided Carrier Phase Recovery for 100G PM-QPSK Digital Coherent Receivers

A feed-forward pilot-symbols aided carrier phase recovery scheme is described. The approach relies on pilot symbols that are time-division multiplexed with the transmitted data. The main advantage of the proposed solution is that of avoiding the phase ambiguity problem after a cycle slip. For homogeneous PM-QPSK transmission the proposed scheme outperforms blind carrier recovery with differential decoding

Photoacoustic Sensing of Trapped Fluids in Nanoporous Thin Films: Device Engineering and Sensing Scheme

Accessing fluid infiltration in nanogranular coatings is an outstanding challenge, of relevance for applications ranging from nanomedicine to catalysis. A sensing platform, allowing to quantify the amount of fluid infiltrated in a nanogranular ultrathin coating, with thickness in the 10 to 40 nm range, is here proposed and theoretically investigated by multiscale modelling. The scheme relies on impulsive photoacoustic excitation of hypersonic mechanical breathing modes in engineered gas-phase synthesised nanogranular metallic ultathin films and time-resolved acousto-optical read-out of the breathing modes frequency shift upon liquid infiltration. A superior sensitivity, exceeding 26x103 cm^2/g, is predicted upon equivalent areal mass loading of a few ng/mm^2. The capability of the present scheme to discriminate among different infiltration patterns is discussed. The platform is an ideal tool to investigate nano fluidics in granular materials and naturally serves as a distributed nanogetter coating, integrating fluid sensing capabilities. The proposed scheme is readily extendable to other nanoscale and mesoscale porous materials.Comment: 14 pages, 4 figure

Highly bactericidal Ag nanoparticle films obtained by cluster beam deposition

Abstract The recent emergence of bacterial pathogens resistant to most or all available antibiotics is among the major global public health problems. As indirect transmission through contaminated surfaces is a main route of dissemination for most of such pathogens, the implementation of effective antimicrobial surfaces has been advocated as a promising approach for their containment, especially in the hospital settings. However, traditional wet synthesis methods of nanoparticle-based antimicrobial materials leave a number of key points open for metal surfaces: such as adhesion to the surface and nanoparticle coalescence. Here we demonstrate an alternative route, i.e. supersonic cluster beam deposition, to obtain antimicrobial Ag nanoparticle films deposited directly on surfaces. The synthesized films are simple to produce with controlled density and thickness, are stable over time, and are shown to be highly bactericidal against major Gram positive and Gram negative bacterial pathogens, including extensively drug-resistant strains. From the Clinical Editor The use of silver nanoparticle in health care is getting more widespread. The authors here describe the technique of cluster beam deposition for spraying silver on surfaces used in health care sectors. This may open a new avenue for future anti-bacterial coatings

Exploring multielement nanogranular coatings to forestall implant-related infections

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 features of both Ti-Ag-Cu and Mg-Ag-Cu coatings, as well as their action in hampering the biofilm formation, highlighting the safe use of the tested multielement families of nanoparticles as new strategies against bacterial attachment to the surface of biomedical implants

Photocatalytic Activity of Cellulose Acetate Nanoceria/Pt Hybrid Mats Driven by Visible Light Irradiation

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

Influence of roughness, porosity and grain morphology on the optical properties of ultrathin Ag films

The dielectric function ε(ω) determines the optical behavior of thin and ultrathin metal films, crucial for many research areas and devices. Surprisingly, even for the paradigmatic case of evaporated Ag films, a large scattering of ε(ω) exists, mainly because the film is modelled by neglecting grain structure and surface roughness. Here, we quantitatively describe the optical - morphological relationships for Ag films in the 5.4 to 63 nm range thermally evaporated on fused silica. The experimental reflectance and transmission spectra are reproduced by a multilayer model employing an effective medium approximation for each layer. For the 9 nm thick film we describe how the film grain size and shape, porosity and surface roughness determine the reflectance and transmission spectra, and the total film ε(ω). Moreover, we provide the thickness dependent trend of the morphology-optical response correlation thus obtaining a complete quantitative description of the Ag films behavior up to the transition to the bulk regime. These results make this work a milestone in the morphology-optical understanding for ultrathin metal films and open new perspectives in the interpretation of thin film properties and in the design of the optical response of a tailored system

The Role of Substrate on Thermal Evolution of Ag/TiO2 Nanogranular Thin Films

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