The synthesis of Co-based two-dimensional (2D) metal azolate framework nanosheets (MAF-5-CoII NS) is described using a simple hydrothermal method. The product was isostructural to MAF-5 (Zn). The as-prepared MAF-5-CoII NS exhibited high surface area (1155 m2/g), purity, and crystallinity. The MAF-5-CoII NS–modified screen-printed electrode (MAF-5-CoII NS/SPE) was used for nonenzymatic detection of glucose in diluted human blood plasma (BP) samples with phosphate buffer saline (PBS, pH 7.4) and NaOH (0.1 M, pH 13.0) solutions. The MAF-5-CoII NS nanozyme displayed good redox activity in both neutral and alkaline media with the formation of CoII/CoIII redox pair, which induced the catalytic oxidation of glucose. Under the optimized detection potential, the sensor presented a chronoamperometric current response for the oxidation of glucose with two wide concentration ranges in PBS-diluted (62.80 to 180 μM and 305 to 8055 μM) and NaOH-diluted (58.90 to 117.6 μM and 180 to 10,055 μM) BP samples, which were within the limit of blood glucose levels of diabetic patients before (4.4–7.2 mM) and after (10 mM) meals (recommended by the American Diabetes Association). The sensor has a limit of detection of ca. 0.25 and 0.05 μM, respectively, and maximum sensitivity of ca. 36.55 and 1361.65 mA/cm2/mM, respectively, in PBS- and NaOH-diluted BP samples. The sensor also displayed excellent stability in the neutral and alkaline media due to the existence of hydrophobic linkers (2-ethyl imidazole) in the MAF-5-CoII NS, good repeatability and reproducibility, and interference-free signals. Thus, MAF-5-CoII NS is a promising nanozyme for the development of the disposable type of sensor for glucose detection in human body fluids.
For the new generation of high intensity hadronic machines as, for instance, LHC, halo collimation is a necessary issue for the accelerator to operate at the highest possible luminosity and to prevent the damage of superconductor magnets.1 We propose an experiment aimed to systematic study of the channeling phenomenology and of the newly observed "volume reflection" effect. This experiment will be performed for an external SPS beamline and will make use of a primary proton beam with 400 GeV/c momentum and very small (∼ 3 μrad) divergence. The advantage of a proposed experiment is precise tracking of particles that interacted with a crystal, so that to determine the single-pass efficiency for all the processes involved. For this purpose, a telescope equipped with high-resolution silicon microstrip detectors will be used. New generation silicon crystals and an extra-precise goniometer are mandatory issues. Main goal of the experiment is to get the precise information on channeling of relativistic particles and, ultimately, on the feasibility of such technique for halo collimation at LHC. In this contribution we review the status of the setting-up of experimental apparatus and its future development in sight of the planned run in September 2006.
For an active hydrogen gas generation through water dissociation, the sluggish oxygen evolution reaction (OER) kinetics due to large overpotential is a main hindrance. Herein, a simple approach is used to produce composite material based on TiO2/Co3O4 for efficient OER and overpotential is linearly reduced with increasing amount of TiO2. The scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) investigations reveal the wire like morphology of composite materials, formed by the self-assembly of nanoparticles. The titania nanoparticles were homogenously distributed on the larger Co3O4 nanoparticles. The powder x-ray diffraction revealed a tetragonal phase of TiO2 and the cubic phase of Co3O4 in the composite materials. Composite samples with increasing TiO2 content were obtained (18%, 33%, 41% and 65% wt.). Among the composites, cobalt oxide-titanium oxide with the highest TiO2 content (CT-20) possesses the lowest overpotential for OER with a Tafel slope of 60 mV dec−1 and an exchange current density of 2.98 × 10−3A/cm2. The CT-20 is highly durable for 45 h at different current densities of 10, 20 and 30 mA/cm2. Electrochemical impedance spectroscopy (EIS) confirmed the fast charge transport for the CT-20 sample, which potentially accelerated the OER kinetics. These results based on a two-step methodology for the synthesis of TiO2/Co3O4 material can be useful and interesting for various energy storage and energy conversion systems.
Quantum dot (QD) sensitized TiO2 is considered as a highly promising photoanode material for photoelectrochemical (PEC) solar hydrogen production. However, due to its limited stability, the photoanode suffers from degradation of its long-term PEC performance. Here, we report the design and characterization of a high-efficiency and long-term stable Pt-free PEC cell. The photoanode is composed of a mesoporous TiO2 nanoparticle film sensitized with “giant” core@shell QDs for PEC solar hydrogen generation. The thick shell enhances light absorption in the visible range, increases the stability of the QDs and does not inhibit charge separation, injection and transport, needed for proper operation of the device. We prepared thin films of Cu2S nanoflakes through a simple and reproducible procedure, and used them as counter-electrodes replacing the standard Pt film, resulting in equivalent performances of the PEC cell. We obtained an unprecedented photocurrent density (~10 mA/cm2) for “giant” QDs based PEC devices (and corresponding H2 generation) and a very promising stability, indicating that the proposed cell architecture is a good candidate for long-term stable QD-based PEC solar hydrogen generation.
The immense progress of humanity on the technological, domestic, and industrial fronts comes at the cost of polluting the planet. Aquatic pollution is particularly dangerous since all life forms are directly linked to it. Each year tons of industrial and domestic pollutants make their way into aqueous systems. Efficient removal/degradation of these pollutants is of prime importance for the sustainable future. Among many technologies, photodegradation is an emerging and promising method for the successful removal of aqueous pollutants since it is powered by abundant solar light. The last decade had shown that carbon dots are among the most promising materials that can be utilized as an efficient tool to derive various solar-driven chemical reactions. Carbon dots possess unique photophysical and chemical properties such as light-harvesting over a broad-spectrum region, upconversion photoluminescence, photosensitizers, chemical inertness, and bivalent redox character, etc. The ease of synthesis of carbon dots at low cost also contributes hugely to their utilizations as an efficient photocatalyst for the degradation of aqueous pollutants. This review summarizes the recent progress made in the field of photodegradation of aqueous pollutants with the aid of carbon dots and their hybrids, highlighting the critical role carbon dots can play in the field.
Ceria-doped titania photocatalysts (ceria loading 0.25–5.0 wt%) were synthesized by hydrothermal methods for water remediation. Nanotubes (CeTNTx) and nanoparticles (CeTNPx) were obtained. Ceria doping was applied to tune the electronic properties of nanostructured titania, boosting its photocatalytic activity. CeTNT nanostructures contained anatase as the only titania phase, whereas the CeTNP series consisted of both anatase and rutile polymorphs. The Ce addition induced a decrease in the energy gap, allowing enhancement of visible light harvesting. The photodegradation of methylene blue, MB, in aqueous solution was chosen to study the influence of the morphology and the ceria loading on the photocatalytic response, under UV and solar light. Both CeO2–TiO2 nanoparticles and nanotubes were found to be very active under UV light. The highest MB degradation rates were obtained for the 0.25 wt% CeO2 doping, for both nanotubes and nanoparticles (0.123 and 0.146 min−1, respectively), able to photodegrade completely the dye after 120 min. The two samples are stable after a 3-cycle reusability test. The photo-response under simulated solar light confirmed that doping titania with ceria allows harvesting visible light absorption, enhancing its photoactivity. A maximum efficiency of 85% under simulated sunlight at a degradation rate of 0.054 min−1 was obtained. Transient photoluminescence confirmed that MB acts as a charge scavenger for the composite system. These results pointed out ceria-doped titania nanostructures as a promising class of photocatalysts for the degradation of dyes and other hazardous organic compounds in wastewater.
Atomic layer deposition (ALD) was used to deposit ZnO/Al2O3/V2O5 nanolaminate coatings to demonstrate a coating system with temperature adaptive frictional behaviour. The nanolaminate coating exhibited excellent conformity and crack-free coating of thickness 110 nm over Inconel 718 substrate. The ALD trilayer coating showed a hardness and elastic modulus of 12 GPa and 193 GPa, respectively. High-temperature tribology of the nanolaminate trilayer was tested against steel ball in dry sliding condition at 25 °C (room temperature, RT), 200 °C, 300 °C, and 400 °C. It was found that the nanolaminate coating showed a low coefficient of friction (COF) and wear rate at RT and 300 °C. The trilayer coating was found intact and stable at all temperatures during the friction tests. The adaptability of nanolaminate coating with the temperature was verified by performing the cyclic friction test at 300 °C and RT. The low COF and wear rate had been attributed to the (100) and (002) basal plane sliding of ZnO top layer, and the interlayer sliding of weakly bonded planes parallel to (001) plane in V2O5 bottom layer. Furthermore, even after the removal of ZnO coating during the tribotest, the bottom V2O5 layer coating stabilized the COF and wear rate at RT and 300 °C.
Development of high-entropy alloy (HEA) films is a promising and cost-effective way to incorporate these materials of superior properties in harsh environments. In this work, a refractory high-entropy alloy (RHEA) film of equimolar CuMoTaWV was deposited on silicon and 304 stainless-steel substrates using DC-magnetron sputtering. A sputtering target was developed by partial sintering of an equimolar powder mixture of Cu, Mo, Ta, W, and V using spark plasma sintering. The target was used to sputter a nanocrystalline RHEA film with a thickness of ∼900 nm and an average grain size of 18 nm. X-ray diffraction of the film revealed a body-centered cubic solid solution with preferred orientation in the (110) directional plane. The nanocrystalline nature of the RHEA film resulted in a hardness of 19 ± 2.3 GPa and an elastic modulus of 259 ± 19.2 GPa. A high compressive strength of 10 ± 0.8 GPa was obtained in nanopillar compression due to solid solution hardening and grain boundary strengthening. The adhesion between the RHEA film and 304 stainless-steel substrates was increased on annealing. For the wear test against the E52100 alloy steel (Grade 25, 700–880 HV) at 1 N load, the RHEA film showed an average coefficient of friction (COF) and wear rate of 0.25 (RT) and 1.5 (300 °C), and 6.4 × 10–6 mm3/N m (RT) and 2.5 × 10–5 mm3/N m (300 °C), respectively. The COF was found to be 2 times lower at RT and wear rate 102 times lower at RT and 300 °C than those of 304 stainless steel. This study may lead to the processing of high-entropy alloy films for large-scale industrial applications.
The inception of high-entropy alloy promises to push the boundaries for new alloy design with unprecedented properties. This work reports entropy stabilisation of an octonary refractory, HfMoNbTaTiVWZr, high-entropy thin film metallic glass, and derived nitride films. The thin film metallic glass exhibited exceptional ductility of ≈60% strain without fracture and compression strength of 3 GPa in micro-compression, due to the presence of high density and strength of bonds. The thin film metallic glass shows thermal stability up to 750 °C and resistance to Ar-ion irradiation. Nitriding during film deposition of HfMoNbTaTiVWZr thin film of strong nitride forming refractory elements results in deposition of nanocrystalline nitride films with compressive strength, hardness, and thermal stability of up to 10 GPa, 18.7 GPa, and 950 °C, respectively. The high amount of lattice distortion in the nitride films leads to its insulating behaviour with electrical conductivity as low as 200 S cm−1 in the as-deposited film. The design and exceptional properties of the thin film metallic glass and derived nitride films may open up new avenues of development of bulk metallic glasses and the application of refractory-based high entropy thin films in structural and functional applications.
We propose a new facile electrochemical sensing platform for determination of urea, based on a glassy carbon electrode (GCE) modified with nickel cobalt oxide (NiCo2O4) nanoneedles. These nanoneedles are used for the first time for highly sensitive determination of urea with the lowest detection limit (1 μM) ever reported for the non-enzymatic approach. The nanoneedles were grown through a simple and low-temperature aqueous chemical method. We characterized the structural and morphological properties of the NiCo2O4 nanoneedles by TEM, SEM, XPS and XRD. The bimetallic nickel cobalt oxide exhibits nanoneedle morphology, which results from the self-assembly of nanoparticles. The NiCo2O4 nanoneedles are exclusively composed of Ni, Co, and O and exhibit a cubic crystalline phase. Cyclic voltammetry was used to study the enhanced electrochemical properties of a NiCo2O4 nanoneedle-modified GCE by overcoming the typical poor conductivity of bare NiO and Co3O4. The GCE-modified electrode is highly sensitive towards urea, with a linear response (R2 = 0.99) over the concentration range 0.01–5 mM and with a detection limit of 1.0 μM. The proposed non-enzymatic urea sensor is highly selective even in the presence of common interferents such as glucose, uric acid, and ascorbic acid. This new urea sensor has good viability for urea analysis in urine samples and can represent a significant advancement in the field, owing to the simple and cost-effective fabrication of electrodes, which can be used as a promising analytical tool for urea estimation.
A facile and efficient electrochemical sensing platform has been successfully exploited for the first time for the determination of lactic acid using a nickel oxide (NiO) nanoparticle-modified glassy carbon electrode (GCE). Nickel oxide nanoparticles were prepared by a chemical growth method using different quantities of arginine as a soft template. The structural and morphological properties of NiO nanoparticles were characterized by Raman spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD). Cyclic voltammetry (CV) was used to study the electrochemical properties of various samples. The modified electrode is highly sensitive and presents a linear response over a wide range (0.005–5 mM) of lactic acid concentrations in 0.1 M NaOH. The detection limit for the sensor was found to be 5.7 μM, and it exhibits good stability. Furthermore, the sensor shows excellent selectivity in the presence of common interfering species. The lactic acid sensor showed good viability for lactic acid analysis in real samples (milk, yogurt and red wine) and demonstrated significant advancement in sensor technology for practical applications.
Nickel oxide (NiO) nanostructures are employed in the basic medium for the oxidation of ethanol. A variety of NiO nanostructures are synthesized by wet chemical growth method, using different hydroxide (OH−) ion sources, particularly from ammonia, hexamethylenetetramine, urea and sodium hydroxide. The use of urea as (OH−) ion source results in flower‐like NiO structures composed by extremely thin nanowalls (thickness lower than 10 nm,), which demonstrated to be the most active for ethanol oxidation. All the samples exhibit NiO cubic phase, and no other impurity was detected. The cyclic voltammetry (CV) curves of NiO nanostructures were found linear over the concentration range 0.1–3.5 mM (R2=0.99) of ethanol, with the limit of detection estimated to be 0.013 mM for ethanol. The NiO nanostructures exhibit a selective signal towards ethanol oxidation in the presence of different members of alcohol family. The proposed NiO nanostructures showed a significant practicality for the reproducible and sensitive determination of ethanol from brandy, whisky, mixture of brandy and rum, and vodka samples. The nanomaterial was used as a surface modifying agent for the glassy carbon electrode and it showed a stable electro‐oxidation activity for the ethanol for 16 days. These findings indicate that the presented NiO nanomaterial can be applied in place of noble metals for ethanol sensing and other environmental applications (like fuel cells).
The ZnO seed layer, acting as nucleation center for the growth of ZnO nanorods (NRs), has strong impact on the optical and photodetection properties of ZnO-based UV photodetectors (PDs). In this paper, vertically aligned ZnO NRs were grown by varying the thickness of the seed layer in the range 50–125 nm, to investigate its influence on the recovery time of the PD. Single crystalline ZnO NRs were obtained as indicated by combined electron microscopy and X-ray diffraction analysis. The photoluminescence (PL) spectra proved that the lowest PL intensity (i.e.: the lowest recombination) belongs to the sample with seed layer thickness of 100 nm (labeled as NR-7). The carrier concentration of ZnO NR films was estimated from the slope of the Mott–Schottky plot. It was 1.49 × 10+20 cm−3 for seed layer thickness of 65 nm (NR-5), which was dramatically reduced to 5.44 × 10+17 cm−3 in the sample NR-9 (seed layer thickness 125 nm). Furthermore, the current-voltage (I-V) and chronoamperometric (I-t) analysis indicate a high UV responsivity under a UV irradiation. The fastest recovery time (0.1 s time decay constant) occurs in sample NR-7 (seed layer 100 nm thick). These results indicate that effective control of the electronic and optical properties in ZnO NRs can be obtained by proper tuning of the seed layer, enabling a simple and straightforward strategy to optimize NR functionality, depending on their planned use.
Channeling of relativistic particles in bent Si crystals is a powerful technique for use with accelerators. Its efficiency can be found to be highly dependent on the state of the surface of the crystal steering the particles. We investigated the morphology and structure of the surface of the samples that have been used with high efficiency for channeling in accelerators. Low-energy channeling of 2 MeVα particles or protons was used as a probe. We found that mechanical treatment of the samples leads to a superficial damaged layer, which is correlated to efficiency limitations of the crystal in accelerators. In contrast, chemical etching, which was used to treat the surface of the most efficient crystals, leaves a surface with superior perfection. © 2005 American Institute of Physics.
The new generation of hadron machines may profitably take advantage of channeling for steering and collimation of high-energy particle beams. In that case, the requirements on the quality of the crystal surface are rather stringent in terms of both lattice perfection and roughness. Here, the authors show the structural and morphological characterizations of crystals fabricated through a method to achieve a surface that fulfills all needed specifications for application in hadron machines. © 2007 American Institute of Physics.
We report the fabrication and testing of dye sensitized solar cells (DSSC) based on tin oxide (SnO2) particles of average size ~20 nm. Fluorine-doped tin oxide (FTO) conducting glass substrates were treated with TiOx or TiCl4 precursor solutions to create a blocking layer before tape casting the SnO2 mesoporous anode. In addition, SnO2 photoelectrodes were treated with the same precursor solutions to deposit a TiO2 passivating layer covering the SnO2 particles. We found that the modification enhances the short circuit current, open-circuit voltage and fill factor, leading to nearly 2-fold increase in power conversion efficiency, from 1.48% without any treatment, to 2.85% achieved with TiCl4 treatment. The superior photovoltaic performance of the DSSCs assembled with modified photoanode is attributed to enhanced electron lifetime and suppression of electron recombination to the electrolyte, as confirmed by electrochemical impedance spectroscopy (EIS) carried out under dark condition. These results indicate that modification of the FTO and SnO2 anode by titania can play a major role in maximizing the photo conversion efficiency
The LUNA (Laboratory Underground for Nuclear Astrophysics) facility has been designed to study nuclear reactions of astrophysical interest. It is located deep underground in the Gran Sasso National Laboratory, Italy. Two electrostatic accelerators, with 50 and 400 kV maximum voltage, in combination with solid and gas target setups allowed to measure the total cross-sections of the radiative-capture reactions 2H2H(p, γ) 3He3Heand 14N14N(p, γ) 15O15Owithin their relevant Gamow peaks. We report on the gamma background in the Gran Sasso laboratory measured by germanium and bismuth germanate detectors, with and without an incident proton beam. A method to localize the sources of beam-induced background using the Doppler shift of emitted gamma rays is presented. The feasibility of radiative-capture studies at energies of astrophysical interest is discussed for several experimental scenarios. © Società Italiana di Fisica/Springer-Verlag 2005.
Metal chalcogenide quantum dots (QDs) are among the most promising materials as light harvesters in all-inorganic systems for applications in solar cells and production of solar fuels. The electronic band structure of composite QDs formed by lead and cadmium chalcogenides directly grafted on highly oriented pyrolytic graphite surfaces through successive ionic layer absorption and reaction is investigated. Atomic force microscopy and Kelvin probe force microscopy (KPFM) are applied to investigate PbS, CdS, and PbS/CdS QD systems. The variation of the surface potential of individual QDs is measured, investigating the evolution of the electronic band structure as a function of QD size and composition. A shift of the Fermi level toward more negative values occurs when QD size is increased. The shift is more pronounced in CdS than in PbS, while the composite PbS/CdS exhibits an intermediate behavior. The calculated shift is in good agreement with the experiments. These results highlight the ability of KPFM to directly measure the electronic band structure in individual QDs of metal chalcogenide composites. This feature regulates charge dynamics in composite systems, thereby affecting device performance. This work provides valuable insights for applications in several fields, in which charge injection plays a major role.
We report on the effects of incorporation of different concentrations of carboxyl group (COOH)-functionalized multi-wall carbon nanotubes (F-MWCNTs) into TiO2 active layers for dye-sensitized solar cells (DSSCs). Standard DSSCs with bare TiO2 exhibit a photo-conversion efficiency (PCE) of 6.05% and a short circuit current density (Jsc) of 13.3 mA cm−2. The presence of 2 wt% F-MWCNTs in the photoanodes increases the PCE up to 7.95% and Jsc up to 17.5 mA cm−2. The photoanodes were characterized using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. The electrochemical behaviour of the solar cells was investigated by electrochemical impedance spectroscopy (EIS). We attribute the improved performances to the combined effect of increased dye loading and reduced charge recombination (as clarified by dye loading and EIS measurements), due to the conformal coverage of F-MWCNTs, which allows fast and efficient charge collection in operating solar cells. These results can help in improving the PCE in DSSCs in an elegant and straightforward way, minimizing the need of additional steps (e.g. pre- and post-treatment with TiCl4) for photoanode preparation.
We report the effect of the integration of carbon dots (Cdots) in high-performance inverted planar-heterojunction (PHJ) perovskite solar cells (PSCs). We used Cdots to modify the hole-transport layer in planar PSC devices. By introducing Cdots on graphene oxide (GO) as hole-transporting layer, the efficiency of the PSC improved significantly from 14.7% in the case of bare GO to 16.2% of the best device with optimized Cdots content. When applying Cdots with an engineered absorption in the UV range as downshifting layer, the device performance was further improved, attaining a maximum PCE of 16.8% (+14%); the stability of the device was also enhanced of more than 20%. Kelvin probe force microscopy (KPFM) and cyclic voltammetry (CV) were employed to analyze the electronic band alignment at the interface between GO/Cdots and the perovskite film. Holes were extracted and transferred to the conductive substrate more efficiently in the presence of Cdots, thus delaying charge recombination. Photoluminescence (PL), transient PL decays and transient photovoltage (TPV) decays investigated the charge-transfer kinetics and proved the retardation of charge recombination. This work reveals an effective enhancement of the performance of planar PSCs by using Cdots/GO as hole transport material.
Designing an efficient electrocatalyst for the oxygen evolution reaction (OER) in alkaline media is highly needed but very challenging task. Herein, we used organic polyelectrolytes such as (carboxymethyl cellulose) CMC and polyacrylamide polymers for the growth of Co3O4 nanostructures by aqueous chemical growth method. The morphology and composition studies were performed on scanning electron microscopy (SEM), energy dispersive X-ray (EDX), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM) techniques. The structural properties and the surface chemistry of the Co3O4 electrocatalysts were correlated to the OER performance, and the enhancement mechanism with respect to pristine Co3O4 was observed to be specifically related to the polyelectrolyte templating role.
Co3O4@CMC composites displayed reduced crystallite size, producing OER overpotential as low as 290 mV at 10 mAcm−2 in 1.0 KOH and Tafel slope of 71 mVdec−1, suggesting fast transfer of intermediates and electrons during water electrolysis. On the other hand, the use of polyacrylamide and its different templating mechanism resulted in similar crystallite size, but preferential exposed faces and larger surface vacancies content, as demonstrated by HR-TEM and XPS, respectively. Consistently, this material displays cutting-edge OER performance, such as overpotential of 260 mV at 10 mAcm−2 and a low Tafel slope of 63 mVdec−1. The proposed strategy for the preparation of Co3O4 nanostructures in the presence of CMC and polyacrylamide is facile, mass production, thus it could equally contributed towards the realization of hydrogen energy. Therefore, these nanostructures of Co3O4 can be regarded as an alternative and promising materials for the different electrochemical applications including fuel cells, metal air batteries, overall water electrolysis and other energy storage devices.
We have investigated the sensing properties of indium oxide nanostructures and tailored the deposition conditions in order to obtain nano-wires of indium oxide. We have comparatively tested the gas sensing properties of nano-wires with micrometric or even nanometric size. The micro-wires feature interesting gas sensitivity at room temperature, particularly in the case of nitrogen dioxide detection. The sensing performance is improved as the lateral dimension of the wire decreases. © 2006 Elsevier B.V. All rights reserved.
We describe a phase-coherent multifrequency lock-in measurement technique that uses the inverse Fourier transform to reconstruct the nonlinear current-voltage characteristic of a nanoscale junction. The method provides separation of the galvanic and displacement currents in the junction and easy cancellation of the parasitic displacement current from the measurement leads. These two features allow us to overcome traditional limitations imposed by the low conductance of the junction and the high capacitance of the leads, thus providing an increase in measurement speed of several orders of magnitude. We demonstrate the method in the context of conductive atomic force microscopy, acquiring current-voltage characteristics at every pixel while scanning at standard imaging speed.
Tetrahedral manganese(II) complexes having formulae [MnX2{O = PR(NMe2)2}2] (X = Br, I; R = NMe2, Ph) were isolated and characterized, and in the case of [MnBr2{O = PPh(NMe2)2}2] the structure was ascertained by means of single crystal X-ray diffraction. All the complexes showed intense green emission assigned to the Mn(II) 4T1(4G) → 6A1(6S) transition upon excitation with UV light, with photoluminescence lifetimes in the range 100–1000 μs. Bromo-complexes maintain their luminescence features once dispersed in polycaprolactone matrix.
The Cu(I) coordination polymer [Cu3(μ3-I)3(μ-btzMe)(NCCH3)]n (btzMe = 1-methyl-1H-benzotriazole) was prepared and characterized by X-Ray diffraction. The compound showed strong green emission upon excitation with wavelengths below 475 nm, with lifetime of 47 μs. The emission was attributed to 3(X,M)LCT transition on the basis of experimental data and DFT calculations.
The sensitization of Eu(III) luminescence by the phosphoramide and arylphosphonic diamide ligands OP(NMe2)2Ind, OP(NMe2)2Cbz, OP(NMe2)2Ph, OP(NMe2)2(1-Naph) and OP(NMe2)2(2-Naph) (Ind = indol-1-yl; Ph = phenyl; Cbz = carbazol-9-yl; 1-Naph = naphtalen-1-yl; 2-Naph = naphtalen-2-yl) was verified by coordination to the [Eu(NO3)3] metal fragment. The emission spectra of the corresponding complexes showed only the 5D0 → 7FJ transitions of the metal centre, with the exception of the carbazolyl derivative. Some of the ligands were also able to sensitize Tb(III) luminescence, in agreement with the triplet state energies estimated from the phosphorescence spectra of the analogous Gd(III) nitrates. On the basis of the photoluminescence results achieved using nitrate as ancillary ligand, heptacoordinate Eu(III) complexes having general formula [Eu(β-dike)3L] (β-dike = dibenzoylmethanate, tenoyltrifluoroacetonate; L = phosphoramide or arylphosphomic diamide ligand) were prepared and characterized. All the complexes exhibited bright red emission upon excitation with near-UV and violet-blue light, with intrinsic quantum yields ranging between 18 and 36%.
Thin films have been grown on silicon and silica substrates by cosputtering of silica and silver in Ar, Ar+2.5% O2, and Ar+5% O2 gas mixtures. Rutherford backscattering spectrometry showed that the films have Ag atomic fractions xAg in the range of ∼1 to ∼10 at. %, and, by valence considerations, that the fraction of oxidized Ag in the films deposited in presence of oxygen is limited. Transmission electron microscopy images revealed the presence of Ag nanoclusters, with a mean size diameter not larger than 5 nm. The clusters are preferentially arranged along columns. It is suggested that the columns are regions with diameter in the nanometer range in which the density of the dielectric matrix is lower, thus favoring the formation of metal clusters. In presence of O2, the clusters were observed to have a more regular spherical shape. The optical absorption spectra of films grown in presence of O2 are distinguished from those grown in Ar by specific features, which are attributed to oxidation at the cluster surface. © 2005 American Vacuum Society.
We explore the potential of Tb- and Yb-doped InVO4, InTaO4, and InNbO4 for applications as phosphors for light-emitting sources. Doping below 0.2% barely change the crystal structure and Raman spectrum but provide optical excitation and emission properties in the visible and near-infrared (NIR) spectral regions. From optical measurements, the energy of the first/second direct band gaps was determined to be 3.7/4.1 eV in InVO4, 4.7/5.3 in InNbO4, and 5.6/6.1 eV in InTaO4. In the last two cases, these band gaps are larger than the fundamental band gap (being indirect gap materials), while for InVO4, a direct band gap semiconductor, the fundamental band gap is at 3.7 eV. As a consequence, this material shows a strong self-activated photoluminescence centered at 2.2 eV. The other two materials have a weak self-activated signal at 2.2 and 2.9 eV. We provide an explanation for the origin of these signals taking into account the analysis of the polyhedral coordination around the pentavalent cations (V, Nb, and Ta). Finally, the characteristic green (5D4 → 7FJ) and NIR (2F5/2 → 2F7/2) emissions of Tb3+ and Yb3+ have been analyzed and explained.
We have studied the electronic properties at ambient pressure and under high pressure of InVO4, InNbO4, and InTaO4 powders, three candidate materials for hydrogen production by means of photocatalytic water splitting using solar energy. A combination of optical absorption and resistivity measurements and band structure calculations have allowed us to determine that these materials are wide band-gap semiconductors with a band-gap energy of 3.62(5), 3.63(5), and 3.79(5) eV for InVO4, InNbO4, and InTaO4, respectively. The last two compounds are indirect band-gap materials, and InVO4 is a direct band-gap material. The pressure dependence of the band-gap energy and the electrical resistivity have been determined too. In the three compounds, the band gap opens under compression until reaching a critical pressure, where a phase transition occurs. The structural transition triggers a band-gap collapse larger than 1.2 eV in the three materials, being the abrupt decrease in the band-gap energy related to an increase in the pentavalent cation coordination number. The phase transitions also cause changes in the electrical resistivity, which can be correlated with changes induced by pressure in the band structure. An explanation to the reported results is provided based upon ab initio calculations. The conclusions attained are of significance for technological applications of the studied oxides.
The structural stability and physical properties of CrVO4 under compression were studied by X-ray diffraction, Raman spectroscopy, optical absorption, resistivity measurements, and ab initio calculations up to 10 GPa. High-pressure X-ray diffraction and Raman measurements show that CrVO4 undergoes a phase transition from the ambient pressure orthorhombic CrVO4-type structure (Cmcm space group, phase III) to the high-pressure monoclinic CrVO4-V phase, which is isomorphic to the wolframite structure. Such a phase transition (CrVO4-type → wolframite), driven by pressure, also was previously observed in indium vanadate. The crystal structure of both phases and the pressure dependence in unit-cell parameters, Raman-active modes, resistivity, and electronic band gap, is reported. Vanadium atoms are sixth-fold coordinated in the wolframite phase, which is related to the collapse in the volume at the phase transition. Besides, we also observed drastic changes in the phonon spectrum, a drop of the band-gap, and a sharp decrease of resistivity. All the observed phenomena are explained with the help of first-principles calculations.
The use of narrow band gap semiconductors such as PbS may expand the light absorption range to the near-infrared region in quantum-dot-sensitized solar cells (QDSCs), increasing the generated photocurrent. However, the application of PbS as a sensitizer in QDSCs causes some problems of stability and high recombination. Here, we show that the direct growth of a CdS coating layer on previously deposited PbS by the simple method of successive ionic layer adsorption and reaction (SILAR) minimizes these problems. A remarkable short-circuit current density for PbS/CdS QDSCs is demonstrated, ∼11 mA/cm2, compared to that of PbS QDSCs, with photocurrents lower than 4 mA/cm2, using polysulfide electrolyte in both cells. The cell efficiency reached a promising 2.21% under 1 sun of simulated irradiation (AM1.5G, 100 mW/cm2). Enhancement of the solar cell performance beyond the arithmetic addition of the efficiencies of the single constituents (PbS and CdS) is demonstrated for the nanocomposite PbS/CdS configuration. PbS dramatically increases the obtained photocurrents, and the CdS coating stabilizes the solar cell behavior. © 2011 American Chemical Society.
Context. The NO cycle takes place in the deepest layer of a H-burning core or shell, when the temperature exceeds T ≈ 30 × 106 K. The O depletion observed in some globular cluster giant stars, always associated with a Na enhancement, may be due to either a deep mixing during the red giant branch (RGB) phase of the star or to the pollution of the primordial gas by an early population of massive asymptotic giant branch (AGB) stars, whose chemical composition was modified by the hot bottom burning. In both cases, the NO cycle is responsible for the O depletion. Aims. The activation of this cycle depends on the rate of the 15N(p, γ)16O reaction. A precise evaluation of this reaction rate at temperatures as low as experienced in H-burning zones in stellar interiors is mandatory to understand the observed O abundances. Methods. We present a new measurement of the 15N(p, γ)16O reaction performed at LUNA covering for the first time the center of mass energy range 70-370 keV, which corresponds to stellar temperatures between 65 × 106 K and 780 × 106 K. This range includes the 15N(p, γ)16O Gamow-peak energy of explosive H-burning taking place in the external layer of a nova and the one of the hot bottom burning (HBB) nucleosynthesis occurring in massive AGB stars. Results. With the present data, we are also able to confirm the result of the previous R-matrix extrapolation. In particular, in the temperature range of astrophysical interest, the new rate is about a factor of 2 smaller than reported in the widely adopted compilation of reaction rates (NACRE or CF88) and the uncertainty is now reduced down to the 10% level. © 2011 ESO.
The brewery industry annually produces huge amounts of byproducts that represent an underutilized, yet valuable, source of biobased compounds. In this contribution, the two major beer wastes, that is, spent grains and spent yeasts, have been transformed into carbon dots (CDs) by a simple, scalable, and ecofriendly hydrothermal approach. The prepared CDs have been characterized from the chemical, morphological, and optical points of view, highlighting a high level of N-doping, because of the chemical composition of the starting material rich in proteins, photoluminescence emission centered at 420 nm, and lifetime in the range of 5.5–7.5 ns. With the aim of producing a reusable catalytic system for wastewater treatment, CDs have been entrapped into a polyvinyl alcohol matrix and tested for their dye removal ability. The results demonstrate that methylene blue can be efficiently adsorbed from water solutions into the composite hydrogel and subsequently fully degraded by UV irradiation.
The photoreduction potential of a set of four different carbon dots (CDs) was investigated. The CDs were synthesized by using two different preparation methods—hydrothermal and pyrolytic—and two sets of reagents—neat citric acid and citric acid doped with diethylenetriamine. The hydrothermal syntheses yielded amorphous CDs, which were either nondoped (a-CDs) or nitrogen-doped (a-N-CDs), whereas the pyrolytic treatment afforded graphitic CDs, either non-doped (g-CDs) or nitrogen-doped (g-N-CDs). The morphology, structure, and optical properties of four different types of CDs revealed significant differences depending on the synthetic pathway. The photocatalytic activities of the CDs were investigated as such, that is, in the absence of any other redox mediators, on the model photoreduction reaction of methyl viologen. The observed photocatalytic reaction rates: a-N-CDs ≥ g-CDs > a-CDs ≥ g-N-CDs were correlated with the presence/absence of fluorophores, to the graphitic core, and to quenching interactions between the two. The results indicate that nitrogen doping reverses the photoredox reactivity between amorphous and graphitic CDs and that amorphous N-doped CDs are the most photoredox active, a yet unknown fact that demonstrates the tunable potential of CDs for ad hoc applications.
The synthesis, characterization and photoreduction ability of a new class of carbon dots made from fish scales is here described. Fish scales are a waste material that contains mainly chitin, one of the most abundant natural biopolymers, and collagen. These components make the scales rich, not only in carbon, hydrogen and oxygen, but also in nitrogen. These self-nitrogen-doped carbonaceous nanostructured photocatalyst were synthesized from fish scales by a hydrothermal method in the absence of any other reagents. The morphology, structure and optical properties of these materials were investigated. Their photocatalytic activity was compared with the one of conventional nitrogen-doped carbon dots made from citric acid and diethylenetriamine in the photoreduction reaction of methyl viologen.
Silver nanoclusters embedded in two transparent fluorinated polyimides, 4,4'-hexafluoroisopropylidene diphthalic anhydride - 2,3,5,6-tetramethyl paraphenylene diamine (6FDA-DAD) and 3,3',4,4' - biphenyltetracarboxylic acid dianhydride - 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane (BPDA-3F), have been produced by surface modification with KOH aqueous solution followed by K-assisted Ag doping and thermal reduction in hydrogen atmosphere. The reaction rate of the nucleophilic hydrolysis in KOH, studied by Fourier transform infrared spectroscopy (FT-IR) and Rutherford backscattering spectrometry (RBS), depends on the polyimide chemical structure. After ion-exchange in AgNO 3 solution and subsequent annealing, the polyimide structure recovery was monitored by FT-IR whereas the characteristic surface plasmon absorption band of silver nanoparticles was evidenced by optical absorption measurements. The structure of silver nanoclusters as related to size and size distribution in the different polyimide matrices was thoroughly investigated by Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The collected data evidenced a uniform distribution of Ag clusters of nanometric size after thermal treatment at 300 °C in both polyimides. For the same ion-exchange treatment parameters and annealing temperature, XRD analyses evidenced the presence of crystallites with similar sizes. © EDP Sciences/Società Italiana di Fisica/Springer-Verlag 2007.
New organic scintillators for ionizing radiation sensors are synthesized by dispersing dye molecules into chemically imidized polyimide hosts in order to obtain detection systems with improved radiation resistance with respect to the traditional polyvinyltoluene-based materials. Nile red (NR) and rhodamine B (RB) are dispersed at different concentrations in polyimides derived from the following monomers: 6FDA-DAD, 6FDA-DAB, and BPDA-3F. Scintillating thin films are produced by the spin coating technique. Scintillation tests are performed both on pure polyimides and on binary systems by means of ion beam induced luminescence (IBIL), in which the emission spectrum is collected during the irradiation of the films with a 4He+ beam. From the intensity and the degradation rate of the IBIL signal during irradiation, the scintillation efficiency with respect to NE102 and the radiation hardness of the produced films are calculated. © 2005 IEEE.
New organic scintillators for ionizing radiation sensors are synthesized by dispersing dye molecules into chemically imidized polyimide hosts in order to obtain detection systems with improved radiation resistance with respect to the traditional polyvinyltoluene based materials. Nile Red and Rhodamine B are dispersed at different concentrations in polyimides derived from the following monomers 6FDA-DAD, 6FDA-DAB and BPDA-3F. Scintillating thin films are produced by the spin coating technique. Scintillation tests are performed both on pure polyimides and on binary systems by means of Ion Beam Induced Luminescence (IBIL), in which the emission spectrum is collected during the irradiation of the films with a 4He+ beam. From the intensity and the degradation rate of the IBIL signal during irradiation, the scintillation efficiency with respect to NE102 and the radiation hardness of the produced films are calculated. © 2004 IEEE.
The continuous evolution of nanotechnology in these years led to the production of quasi-one dimensional (Q1D) structures in a variety of morphologies such as nanowires, core-shell nanowires, nanotubes, nanobelts, hierarchical structures, nanorods, nanorings. In particular, metal oxides (MOX) are attracting an increasing interest for both fundamental and applied science. MOX Q1D are crystalline structures with well-defined chemical composition, surface terminations, free from dislocation and other extended defects. In addition, nanowires may exhibit physical properties which are significantly different from their coarse-grained polycrystalline counterpart because of their nanosized dimensions. Surface effects dominate due to the increase of their specific surface, which leads to the enhancement of the surface related properties, such as catalytic activity or surface adsorption: key properties for superior chemical sensors production. High degree of crystallinity and atomic sharp terminations make nanowires very promising for the development of a new generation of gas sensors reducing instabilities, typical in polycrystalline systems, associated with grain coalescence and drift in electrical properties. These sensitive nanocrystals may be used as resistors, and in FET based or optical based gas sensors. This article presents an up-to-date review of Q1D metal oxide materials research for gas sensors application, due to the great research effort in the field it could not cover all the interesting works reported, the ones that, according to the authors, are going to contribute to this field's further development were selected and described. © 2008 Elsevier Ltd. All rights reserved.
Quasi-one-dimensional nanostructures of tin oxide were produced in controlled conditions through condensation from the vapor phase. The preparation was assisted by noble metal catalysts and uniform single-crystalline nanowires were produced. The nucleation of nanowires was achieved at 470 °C, owing to the vapor-liquid-solid growth mechanism activated by the catalytic Pt clusters. The peculiar microstructural properties of these semiconducting metal oxide nanostructures will be summarized. The high aspect ratio and the high degree of crystallinity achieved for the nanowires foresee their functional exploitation. © 2007 Springer-Verlag.
Effects of iron introduction in RGTO prepared tin oxide gas sensors are presented. The films were deposited by sputtering from a tin target with the introduction of an adjustable number or iron inset. Iron content was varied in the range 0-7%. The thin films are investigated by the volt-amperometric technique for electrical and gas-sensing properties. The layers are capable of sensing CO and ethanol, no evidence of surface poisoning is detected, and recovery of the resistance is complete. The response of the sensors is stable and reproducible at all operating temperatures tested (200-500 °C) during 3 months of operation. © 2005 Elsevier B.V. All rights reserved.
This paper focuses on the capabilities and development prospects of nanostructured metal oxides (MOX) representing the most versatile and richest class of materials in terms of electronic structure and structural, chemical, and physical properties. MOX nano-materials with controlled composition, surface terminations, and crystalline structures to be used as chemical sensors as a new area in analytical chemistry and instrument engineering are discussed. Their principles of operation, and basic characteristics are outlined and main applications of MOX sensor technology are presented. © 2012 Elsevier B.V. All rights reserved.
Interest in nanowires of metal oxide oxides has been exponentially growing in the last years, due to the attracting potential of application in electronic, optical and sensor field. We have focused our attention on the sensing properties of semiconducting nanowires as conductometric and optical gas sensors. Single crystal nanostructures In2O3, SnO 2, and ZnO were synthesized to explore and study their capability in form of multi-nanowires sensors. © 2006 IEEE.
Quasi one-dimensional nanowires of metal oxides are promising for the development of nano-devices. Sn, In, and Zn oxides were produced in form of single-crystalline nanowires through condensation from vapor phase. Furthermore longitudinal and radial heterostructures have been prepared. Nanowires growth occurs in controlled condition and allows the exploitation of size reduction effects on the electrical response to gases. Preparation, microstructural, morphological and electrical characterizations of nanowires are presented and the peculiarities of these innovative structures are highlighted. © 2009 Elsevier B.V. All rights reserved.
Thin films of titania with the addition of niobium and tantalum have been achieved by reactive sputtering process. Structural and morphological studies have been carried out by means of XRD, RBS, TEM and AFM in order to correlate the microstructural features to the sensing performance of the layers. The films proved sensitive to ethanol and carbon monoxide and ammonia. In the case of niobium addition, it was shown that annealing temperature and niobium content strongly influence the gas response of the films converting a n-type response, which is typical of pure TiO2 and of most of metal-oxide sensors, to a p-type response; this peculiarity is crucial for the discrimination of different gases. In the case of tantalum addition, the annealing treatment at 800 °C led only to a phase transformation that reduced the sensing performance of the layer. High sensitivity to CO is achieved with anatase or mixed anatase and rutile phases, while the rutile phase only exhibit a low gas sensitivity. © 2005 Elsevier B.V. All rights reserved.
Metal oxide (MOx) semiconducting nanostructures hold the potential for playing a critical role in the development of a new platform for renewable energies, including energy conversion and storage through photovoltaic effect, solar fuels, and water splitting. Earth-abundant MOx nanostructures can be prepared through simple and scalable routes and integrated in operating devices, which enable exploitation of their outstanding optical, electronic, and catalytic properties. In this review, the latest research results in this field are illustrated, highlighting the versatility of MOx nanostructures in meeting the stringent requirements to boost the efficiency of different systems. The functional properties inherently correlate to the morphology and the crystalline habit of MOx, which in most of the cases are organized in complex heterostructures. Tailoring the assembly of heterojunctions and their electronic band structure, the catalytic surface properties and the charge transport through complex networks represent the main challenge for the transition of MOx from the research to the real-life in the field of energy conversion and storage.
Semiconducting metal oxide nanostructures represent an appealing class of materials to be applied as efficient electrodes in electrochemical and photoelectrochemical water splitting and in photovoltaics. In article number 1700706, Isabella Concina, Zafar Hussain Ibupoto, and Alberto Vomiero review the latest achievements in the field, illustrating how the structural and functional properties of metal oxides and metal oxide composites can be optimized for targeted applications.