Novel TiO2-Supported Gold Nanoflowers for Efficient Photocatalytic NOx Abatement.

In this study, we pioneered the synthesis of nanoflower-shaped TiO2-supported Au photocatalysts and investigated their properties. Au nanoflowers (Au NFs) were prepared by a Na-citrate and hydroquinone-based preparation method, followed by wet impregnation of the derived Au NFs on the surface of TiO2 nanorods (TNR). A uniform and homogeneous distribution of Au NFs was observed in the TNR + NF(0.7) sample (lower Na-citrate concentration), while their distribution was heterogeneous in the TNR + NF(1.4) sample (higher Na-citrate concentration). The UV-Vis DR spectra revealed the size- and shape-dependent optical properties of the Au NFs, with the LSPR effect observed in the visible region. The solid-state EPR spectra showed the presence of Ti3+, oxygen vacancies and electron interactions with organic compounds on the catalyst surface. In the case of the TNR + NF(0.7) sample, high photocatalytic activity was observed in the H2-assisted reduction of NO2 to N2 at room temperature under visible-light illumination. In contrast, the TNR + NF(1.4) catalyst as well as the heat-treated samples showed no ability to reduce NO2 under visible light, indicating the presence of deformed Au NFs limiting the LSPR effect. These results emphasized the importance of the choice of synthesis method, as this could strongly influence the photocatalytic activity of the Au NFs.

Nanosculptured tungsten oxide: High-efficiency SERS sensor for explosives tracing.

The accurate and rapid identification of explosives and their toxic by-products is an important aspect of safety protocols, forensic investigations and pollution studies. Herein, surface-enhanced Raman scattering (SERS) is used to detect different explosive molecules using an improved substrate design by controllable oxidation of the tungsten surface and deposition of Au layers. The resulting furrow-like morphology formed at the intersection of the tungsten Wulff facets increases nanoroughness and improves the SERS response by over 300 % compared to the untreated surface. The substrate showed excellent reproducibility with a relative standard deviation of less than 15 % and a signal recovery of over 95 % after ultrafast Ar/O2 plasma cleanings. The detection limit for the "dried on a surface" measurement case was better than 10-8 M using the moving scanning regime and an acquisition time of 10 s, while for the "water droplets on a surface" scenario the LoD is 10-7, which is up to 2 orders of magnitude better than the UV-Vis spectroscopy method. The substrates were successfully used to classify the molecular fingerprints of HMX, Tetryl, TNB and TNT, demonstrating the efficiency of a sensor for label-free SERS screening in the practice of monitoring traces of explosives in the water medium.

Plasma-Driven Tuning of Dielectric Permittivity in Graphene.

Materials with tunable negative electromagnetic performance, i.e., where dielectric permittivity becomes negative, have long been pursued in materials research due to their peculiar electromagnetic (EM) characteristics. Here, this promising feature is reported in materials on the case of plasma-synthesized nitrogen-doped graphene sheets with tunable permittivity over a wide (1-40 GHz) frequency range. Selectively incorporated nitrogen atoms in a graphene scaffold tailor the electronic structure in a way that provides an ultra-low energy (0.5-2 eV) 2D surface plasmon excitation, leading to subunitary and negative dielectric constant values in the Ka-band, from 30 up to 40 GHz. By allowing the tailoring of structures at atomic scale, this novel plasma-based approach creates a new paradigm for designing 2D nanomaterials like nanocarbons with controllable and tunable permittivity, opening a path to the next generation of 2D metamaterials.

Threshold Switching in Forming-Free Anodic Memristors Grown on Hf-Nb Combinatorial Thin-Film Alloys.

The development of novel materials with coexisting volatile threshold and non-volatile memristive switching is crucial for neuromorphic applications. Hence, the aim of this work was to investigate the memristive properties of oxides in a Hf-Nb thin-film combinatorial system deposited by sputtering on Si substrates. The active layer was grown anodically on each Hf-Nb alloy from the library, whereas Pt electrodes were deposited as the top electrodes. The devices grown on Hf-45 at.% Nb alloys showed improved memristive performances reaching resistive state ratios up to a few orders of magnitude and achieving multi-level switching behavior while consuming low power in comparison with memristors grown on pure metals. The coexistence of threshold and resistive switching is dependent upon the current compliance regime applied during memristive studies. Such behaviors were explained by the structure of the mixed oxides investigated by TEM and XPS. The mixed oxides, with HfO2 crystallites embedded in quasi amorphous and stoichiometrically non-uniform Nb oxide regions, were found to be favorable for the formation of conductive filaments as a necessary step toward memristive behavior. Finally, metal-insulator-metal structures grown on the respective alloys can be considered as relevant candidates for the future fabrication of anodic high-density in-memory computing systems for neuromorphic applications.

Bacterial DNA Recognition by SERS Active Plasma-Coupled Nanogold.

It is shown that surface-enhanced Raman spectroscopy (SERS) can identify bacteria based on their genomic DNA composition, acting as a "sample-distinguishing marker". Successful spectral differentiation of bacterial species was accomplished with nanogold aggregates synthesized through single-step plasma reduction of the ionic gold-containing vapored precursor. A high enhancement factor (EF = 107) in truncated coupled plasmonic particulates allowed SERS-probing at nanogram sample quantities. Simulations confirmed the occurrence of the strongest electric field confinement within nanometric gaps between gold dimers/chains from where the molecular fingerprints of bacterial DNA fragments gained photon scattering enhancement. The most prominent Raman modes linked to fundamental base-pair molecular vibrations were deconvoluted and used to proceed with nitrogenous base content estimation. The genomic composition (percentage of guanine-cytosine and adenine-thymine) was successfully validated by third-generation sequencing using nanopore technology, further proving that the SERS technique can be employed to swiftly specify bioentities by the discriminative principal-component statistical approach.

CO2 Activation over Nanoshaped CeO2 Decorated with Nickel for Low-Temperature Methane Dry Reforming.

Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into H2 and CO (syngas). CeO2 nanorods, nanocubes, and nanospheres were decorated with 1-4 wt % Ni. The materials were structurally characterized using TEM and in situ XANES/EXAFS. The CO2 activation was analyzed by DFT and temperature-programmed techniques combined with MS-DRIFTS. Synthesized CeO2 morphologies expose {111} and {100} terminating facets, varying the strength of the CO2 interaction and redox properties, which influence the CO2 activation. Temperature-programmed CO2 DRIFTS analysis revealed that under hydrogen-lean conditions mono- and bidentate carbonates are hydrogenated to formate intermediates, which decompose to H2O and CO. In excess hydrogen, methane is the preferred reaction product. The CeO2 cubes favor the formation of a polydentate carbonate species, which is an inert spectator during DRM at 500 °C. Polydentate covers a considerable fraction of ceria's surface, resulting in less-abundant surface sites for CO2 dissociation.

Impact of Electrolyte Incorporation in Anodized Niobium on Its Resistive Switching.

The aim of this study was to develop memristors based on Nb2O5 grown by a simple and inexpensive electrochemical anodization process. It was confirmed that the electrolyte selection plays a crucial role in resistive switching due to electrolyte species incorporation in oxide, thus influencing the formation of conductive filaments. Anodic memristors grown in phosphate buffer showed improved electrical characteristics, while those formed in citrated buffer exhibited excellent memory capabilities. The chemical composition of oxides was successfully determined using HAXPES, while their phase composition and crystal structure with conductive filaments was assessed by TEM at the nanoscale. Overall, understanding the switching mechanism leads towards a wide range of possible applications for Nb memristors either as selector devices or nonvolatile memories.

Degradation of asbestos - Reinforced water supply cement pipes after a long-term operation.

Potable water supply system in major countries still uses a large proportion of asbestos-cement (AC) pipes for fresh drinking water delivery. Generally, after installation and initial purging, the AC tubes are believed to self-passivate by calcite scale and bio-film, especially when conveying hard water. However, the overall performance of AC tubes after decades of operation is significantly reduced and is still mainly unknown. In the current research, we investigated the AC water supply tube after 56 years of operation with high-hardness conveyed water. Our results show that asbestos fibres are emitted from degraded AC pipes as a result of wall softening due to calcium leaching from hydrated cementitious materials, resulting in the loss of mechanical stability. Although the water pumped into the system is not considered aggressive, the seasonal variations of water temperature and chemistry results in an interplay of calcite scaling and Ca leaching, the latter being the dominating process. By comparing the experimental observations with the long-term chemistry reports of the water supplied through the pipes, a positive relationship was established between the temperature and quality of the conveyed water with the corrosion and the calcite scale formation, which are dictating the emission of the fibres into the drinking water. In addition to the health risks posed by asbestos, these processes have many adverse effects on drinking water supply, such as pipe malfunction and destruction resulting in water loss, reduction of hydraulic capacity, microbial proliferation, and water quality deterioration, a topic of interest for global water industries process.

Label-Free Mycotoxin Raman Identification by High-Performing Plasmonic Vertical Carbon Nanostructures.

Mycotoxins are widespread chemical entities in the agriculture and food industries that can induce cancer growth and immune deficiency, posing a serious health threat for humankind. These hazardous compounds are produced naturally by various molds (fungi) that contaminate different food products and can be detected in cereals, nuts, spices, and other food products. However, their detection, especially at minimally harmful concentrations, remains a serious analytical challenge. This research shows that high-performing plasmonic substrates (analytical enhancement factor = 5 × 107 ) based on plasma-grown vertical hollow carbon nanotubes can be applied for immediate detection of the most toxic mycotoxins. Due to excellent sensitivity allowing operation at ppb concentrations, it is possible to collect vibrational fingerprints of aflatoxin B1 , zearalenone, alternariol, and fumonisin B1 , highlighting the key spectral differences between them using principal component analysis. Regarding time-consuming conventional methods, including thin-layer chromatography, gas chromatography, high-performance liquid chromatography, and enzyme-linked immunosorbent assay, the designed surface-enhanced Raman spectroscopy substrates provide a clear roadmap to reducing the detection time-scale of mycotoxins down to seconds.

Advanced Carbon-Nickel Sulfide Hybrid Nanostructures: Extending the Limits of Battery-Type Electrodes for Redox-Based Supercapacitor Applications.

Transition-metal sulfides combined with conductive carbon nanostructures are considered promising electrode materials for redox-based supercapacitors due to their high specific capacity. However, the low rate capability of these electrodes, still considered "battery-type" electrodes, presents an obstacle for general use. In this work, we demonstrate a successful and fast fabrication process of metal sulfide-carbon nanostructures ideal for charge-storage electrodes with ultra-high capacity and outstanding rate capability. The novel hybrid binder-free electrode material consists of a vertically aligned carbon nanotube (VCN), terminated by a nanosized single-crystal metallic Ni grain; Ni is covered by a nickel nitride (Ni3N) interlayer and topped by trinickel disulfide (Ni3S2, heazlewoodite). Thus, the electrode is formed by a Ni3S2/Ni3N/Ni@NVCN architecture with a unique broccoli-like morphology. Electrochemical measurements show that these hybrid binder-free electrodes exhibit one of the best electrochemical performances compared to the other reported Ni3S2-based electrodes, evidencing an ultra-high specific capacity (856.3 C g-1 at 3 A g-1), outstanding rate capability (77.2% retention at 13 A g-1), and excellent cycling stability (83% retention after 4000 cycles at 13 A g-1). The remarkable electrochemical performance of the binder-free Ni3S2/Ni3N/Ni@NVCN electrodes is a significant step forward, improving rate capability and capacity for redox-based supercapacitor applications.

Performances and Biosensing Mechanisms of Interdigitated Capacitive Sensors Based on the Hetero-mixture of SnO2 and In2O3.

This study aims to discuss the synthesis and fabrication of SnO2-In2O3-based thick-films and their biosensing applications. The structural characterization of SnO2-In2O3 nanocomposites was performed using X-ray diffraction, Raman spectroscopy and transmission electron microscopy. Furthermore, the screen-printing technology was used in the fabrication of conductive electrodes to form an interdigitated capacitive structure, and the sensor layer based on the mixture of SnO2 and In2O3. Moreover, the sensing performance of the developed structure was tested using Pseudomonas aeruginosa (P. aeruginosa) and Staphylococcus aureus (S. aureus) bacteria. In addition, the validation of sensing characteristics was performed by electrochemical impedance spectroscopic and self-resonant frequency analysis. Finally, the sensing properties were analyzed for two consecutive days, and changes in both P. aeruginosa and S. aureus pathogens growing media were also studied.

Photodegradation of Methylene Blue and Rhodamine B Using Laser-Synthesized ZnO Nanoparticles.

In this paper we examined the photocatalytic efficiency of a laser-synthesized colloidal solution of ZnO nanoparticles synthesized by laser ablation in water. The average size of the obtained colloidal ZnO nanoparticles is about 47 nm. As revealed by electron microscopy, other nanostructures were also present in the colloidal solution, especially nanosheets. A photocatalytic degradation of UV-irradiated Methylene Blue and Rhodamine B solutions of different concentration in the presence of different ZnO catalyst mass concentrations was studied in order to examine their influence on photodegradation rates. ZnO nanoparticles have shown high photocatalytic efficiency, which is limited due to different effects related to UV light transmittivity through the colloidal solution. Therefore, increasing catalyst concentration is effective way to increase photocatalytic efficiency up to some value where photodegradation rate saturation occurs. The photodegradation rate increases as the dye concentration decreases. These findings are important for water purification applications of laser-synthesized ZnO nanoparticles.

Oriented Carbon Nanostructures from Plasma Reformed Resorcinol-Formaldehyde Polymer Gels for Gas Sensor Applications.

Oriented carbon nanostructures (OCNs) with dominant graphitic characteristics have attracted research interest for various applications due to the excellent electrical and optical properties owing to their vertical orientation, interconnected structures, electronic properties, and large surface area. Plasma enhanced chemical vapor deposition (PECVD) is considered as a promising method for the large-scale synthesis of OCNs. Alternatively, structural reformation of natural carbon precursor or phenol-based polymers using plasma-assisted surface treatment is also considered for the fabrication of OCNs. In this work, we have demonstrated a fast technique for the synthesis of OCNs by plasma-assisted structure reformation of resorcinol-formaldehyde (RF) polymer gels using radio-frequency inductively coupled plasma (rf-ICP). A thin layer of RF polymer gel cast on a glass substrate was used as the carbon source and treated with rf plasma under different plasma discharge conditions. Argon and hydrogen gases were used in surface treatment, and the growth of carbon nanostructures at different discharge parameters was systematically examined. This study explored the influence of the gas flow rate, the plasma power, and the treatment time on the structural reformation of polymer gel to produce OCNs. Moreover, the gas-sensing properties of as-prepared OCNs towards ethanol at atmospheric conditions were also investigated.

Electrochemical immunosensor functionalized with nanobodies for the detection of the toxic microalgae Alexandrium minutum using glassy carbon electrode modified with gold nanoparticles.

In this work an electrochemical immunosensor for the toxic microalgae Alexandrium minutum (A. minutum AL9T) detection is described. A glassy carbon electrode (GCE) was modified by depositing gold nanoparticles followed by L-cysteine for obtaining a self-assembled monolayer. The SpyTagged nanobody C1, specific for the A. minutum toxic strain AL9T, was then covalently immobilized via SpyCatcher on the surface of the modified electrode and used for the selective capture of such microalgae strain. Electrochemical impedance spectroscopy (EIS) was used for the quantification of A. minutum cells present in water samples by measuring the charge-transfer resistance changes of the electrode with a hexacyanoferrate probe. Each electrode modification step was accompanied by cyclic voltammetry (CV) and scanning electron microscopy (SEM). The immunosensor provided highly reproducible data, was simple to fabricate at low cost, exhibited higher sensitivity than previously described alternative diagnostic methods and showed a broad linear range between 103 and 109 cells L-1 with detection limit of 3 × 103 cells L-1 of A. minutum AL9T. The immunosensor was successfully applied to quantify A. minutum AL9T in seawater and brackish water samples proving that it can be used for early detection of harmful microalgae without the necessity of pre-concentration or dialysis steps.

Single-Crystalline Metal Oxide Nanostructures Synthesized by Plasma-Enhanced Thermal Oxidation.

To unravel the influence of the temperature and plasma species on the growth of single-crystalline metal oxide nanostructures, zinc, iron, and copper foils were used as substrates for the study of nanostructure synthesis in the glow discharge of the mixture of oxygen and argon gases by a custom-made plasma-enhanced horizontal tube furnace deposition system. The morphology and microstructure of the resulting metal oxide nanomaterials were controlled by changing the reaction temperature from 300 to 600 °C. Experimentally, we confirmed that single-crystalline zinc oxide, copper oxide, and iron oxide nanostructures with tunable morphologies (including nanowires, nanobelts, etc.) can be successfully synthesized via such procedure. A plausible growth mechanism for the synthesis of metal oxide nanostructures under the plasma-based process is proposed and supported by the nanostructure growth modelling. The results of this work are generic, confirmed on three different types of materials, and can be applied for the synthesis of a broader range of metal oxide nanostructures.

TiN-Nanoparticulate-Reinforced ZrO2 for Electrical Discharge Machining.

This study presents a fabrication route for an electrically conductive ZrO2-TiN ceramic nanocomposite with a nanoscale TiN phase occupying ≤30 vol% to improve the mechanical reinforcement of the zirconia matrix, and at the same time provide electrical conductivity to facilitate electro-discharge machining (EDM). The TiN nanoparticles were incorporated into a 3 mol% yttria-stabilized tetragonal zirconia (Y-TZP) powder, either by admixing a TiN nanopowder (MCP) or by using in-situ synthesis (ISS) via the forced hydrolysis of a titanyl sulphate aqueous solution and the direct nitriding of as-synthesized titania nanoparticles, followed by consolidation and rapid sintering in a spark plasma sintering (SPS) system. The initial phase composition and crystal structure of the as-synthesized powders and the sintered samples were characterized by transmission electron microscopy (TEM) and X-ray difraction (XRD). The influence of the different fabrication routes on the microstructural evolution, electrical and mechanical properties, and affinity for EDM were assessed using TEM, focused ion beam scanning electron microscopy (FIB-SEM, Vickers indentation, electrical conductivity measurements, and profilometry. The MCP synthesis route resulted in finer microstructures that are less prone to microstructural inhomogeneities; however, using the ISS route, it was possible to fabricate electrically conductive Y-TZP nanocomposites containing only 15 vol% of the TiN nanoparticulate phase. Both synthesis routes resulted in an increase of the fracture toughness with an increase of the TiN phase due to the nanoparticulate TiN reinforcement of the Y-TZP ceramic matrix via crack-bridging toughening mechanisms. As both synthesis routes yielded Y-TZP nanocomposites capable of successful EDM machining at a TiN content of ≥30 vol% for the MCP and ≥ 15 vol% TiN for the ISS, a possible mechanism was developed based on the microstructure evolution and grain growth.

Stress Evolution during Ge Nanoparticles Growth in a SiO2 Matrix.

Superstructures are explored that were obtained by multilayer magnetron deposition at room temperature of 20 SiO2 and SiO2:Ge bilayers, each 2 × 4 nm thick, and subsequently annealed in inert N2 atmosphere at different temperatures in the range of 500-750 °C. The structural and optical changes induced by annealing and the formation and growth of Ge nanoparticles (nps) from early clusters to their full growth and final dissolution were studied by the simultaneous grazing-incidence small- and wide-angle X-ray scattering, transmission electron microscopy, and (time-resolved) photoluminescence (PL). It is shown that in as-deposited multilayers aggregation of small clusters already occurred, and the clusters were reasonably well intercorrelated in the lateral plane. During annealing at Ta = 550 °C or higher temperatures, Ge nps start to form and remain partly amorphous at lower Ta but crystallize completely at about 600 °C. At even higher temperatures, the Ge nps dissolve and Ge diffuses out almost completely, leaving voids in the SiO2 matrix. Visible PL from the samples was detected and attributed to defects in the nps/matrix interface layers rather than to the nps itself because PL persisted even after Ge nps dissolution.

Synthesis and characterization of the thermally reduced graphene oxide in argon atmosphere, and its application to construct graphene paste electrode as a naptalam electrochemical sensor.

New insight into the preparation of sensitive carbon-based electrochemical electrode is provided by examining the properties of thermally reduced graphene oxide (TRGO). In this paper, TRGO was prepared by thermal reduction of graphene oxide (GO) in argon atmosphere, and characterized by Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), selected area electron diffraction (SAED), and atomic force microscopy (AFM). Results showed that thermal reduction in argon was effective to remove oxygen-containing functional groups in GO, and graphene sheets were obtained. Furthermore, TRGO was used to prepare thermally reduced graphene oxide paste electrode (TRGOPE) which showed excellent conductivity and fast electron transfer kinetics confirmed by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The electrode was applied to determination of the pesticide naptalam (Nap) in square-wave voltammetric (SWV) mode. The corresponding current at approx. +1.0 V increased linearly with the Nap concentration within two linear dynamic ranges (LDR) of 0.1-1.0 µmol L-1 (LDR1) and 1.0-10.0 µmol L-1 (LDR2). The limits of detection (LOD) and quantification (LOQ) for Nap were calculated as 0.015 µmol L-1 and 0.051 µmol L-1, respectively. In comparison to the carbon paste electrode (CPE) the results showed that the TRGOPE possesses advantages in terms of linearity, sensitivity and detectability.

Improved electron-hole separation and migration in anatase TiO2 nanorod/reduced graphene oxide composites and their influence on photocatalytic performance.

The as-synthesized TiO2 nanorods a-TNR (amorphous TiO2 layer covering the crystalline anatase TiO2 core) and TNR (fully crystalline anatase TiO2) were decorated with reduced graphene oxide (rGO) to synthesize two series of TiO2 + rGO composites with different nominal loadings of GO (from 4 to 20 wt%). The structural, surface and electronic properties of the obtained TiO2 + rGO composites were analyzed and correlated to their performance in the photocatalytic oxidation of aqueous bisphenol A solution. X-ray photoelectron spectroscopy (XPS) analyses revealed that charge separation in TiO2 + rGO composites is improved due to the perfect matching of TiO2 and rGO valence band maxima (VBM). Cyclic voltammetry (CV) experiments revealed that the peak-to-peak separations (ΔEp) are the lowest and the oxidation current densities are the highest for composites with a nominal 10 wt% GO content, meaning that it is much easier for the charge carriers to percolate through the solid, resulting in improved charge migration. Due to the high charge carrier mobility in rGO and perfect VBM matching between TiO2 and rGO, the electron-hole recombination in composites was suppressed, resulting in more electrons and holes being able to participate in the photocatalytic reaction. rGO amounts above 10 wt% decreased the photocatalytic activity; thus, it is critical to optimize its amount in the TiO2 + rGO composites for achieving the highest photocatalytic activity. BPA degradation rates correlated completely with the results of the CV measurements, which directly evidenced improved charge separation and migration as the crucial parameters governing photocatalysis.

Effect of the Cation Distribution and Microstructure on the Magnetic Behavior of the CoMn2O4 Oxide.

The sizes of CoMn2O4 nanoparticles can easily be tuned, from 40 to 8 nm, depending on the temperature of decomposition of the single-source molecular precursor {[Co(bpy)3][Mn2(C2O4)3]·H2O}n. The structural features of the CoMn2O4 spinel are also affected by the heat treatment temperature, showing a pronounced expansion of unit cell parameters as a consequence of thermally induced cation redistribution between tetrahedral and octahedral sites. Moreover, the magnetic behavior of CoMn2O4 was successfully tailored as well; depending on the heat treatment, it is possible to switch between the superparamagnetic and ferrimagnetic ordering and to tailor the magnetic transition temperatures, i.e., the boundaries between the hard and soft magnetic behavior.