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Making a consistency with the objectives of circular economy, herein, waste pistachios shells were utilized for the development of hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) electrocatalysts which are the key bottleneck in the technological evolution of electrolyzers and fuel cells, respectively. As an alternative to scarce and expensive platinum-group-metal (PGM) electrocatalysts, metal nitrogen carbons (MNCs) are emerging as a promising candidate for both aforementioned electrocatalysis where iron and nickel are the metal of choice for ORR and HER, respectively. Therefore, FeNCs and NiNCs were fabricated utilizing inedible pistachio shells as a low-cost biosource of carbon. The steps involved in the fabrication of electrocatalyst were correlated with electrochemical performance in alkaline media. Encouraging onset potential of ~ 0.88 V vs RHE with a possibility of a 2 + 2 reaction pathway was observed in pyrolyzed and ball-milled FeNC. However, HF etching for template removal slightly affected the kinetics and eventually resulted in a relatively higher yield of peroxide. In parallel, the pyrolyzed NiNC demonstrated a lower HER overpotential of ~ 0.4 V vs RHE at − 10 mA cm−2. Nevertheless, acid washing adversely affected the HER performance and consequently, very high overpotential was witnessed.

Among the materials for the negative electrodes in Li-ion batteries, oxides capable of reacting with Li+ via intercalation/conversion/alloying are extremely interesting due to their high specific capacities but suffer from poor mechanical stability. A new way to design nanocomposites based on the Ti/SnOx system is the partial oxidation of the tin-containing MAX phase of Ti3Al(1-x)SnxO2 composition. Exploiting this strategy, we develop composite electrodes of Sn/TiOx and MAX phase capable of withstanding over 600 cycles in half cells with charge efficiencies higher than 99.5% and specific capacities comparable to those of graphite and higher than lithium titanate (Li4Ti5O12) electrodes. These unprecedented electrochemical performances are also demonstrated at full cell level in the presence of a low cobalt content layered oxide and explained through an accurate chemical, morphological and structural investigation which reveals the intimate contact between the MAX phase and the oxide particles. During the oxidation process, electroactive nanoparticles of TiO2 and Ti(1-y)SnyO2 nucleate on the surface of the unreacted MAX phase which therefore acts both as a conductive agent and as a buffer to preserve the mechanical integrity of the oxide during the lithiation and delithiation cycles.

The use of glassceramics in photocatalysis is an attractive option for the realization of smart optical fibers and self-cleaning windows. Here we present the photocatalytic activity of germanosilicate glasses embedding Ga2O3 nanocrystals prepared by batch melting and glass heat treatment. The powdered material is used for UV-assisted degradation of rhodamine in water. The kinetics show changes after repeated experiments. In the first cycle, the apparent rate is governed by a second-order reaction with a Gaussian-like shape, whereas the second cycle follows a first-order reaction. The modification appears to be correlated with perturbations in the defect population. Photoluminescence has been used to monitor the evolution of such defects. Kinetic data on photoreactions and defect formation have been modelled in a combined frame in which the defect concentration determines the photocatalytic activity. The results prove the photocatalytic ability of the studied glassceramics. Moreover, the general validity of the kinetic model can be of interest for other systems in which the photocatalytic response depends on photoreactive species concentration.

Metal-nitrogen-carbons (M-N-Cs) as a reliable substitution for platinum-group-metals (PGMs) for oxygen reduction reaction (ORR) are emerging candidates to rationalize the technology of fuel cells. The development of M-N-Cs can further be economized by consuming waste biomass as an inexpensive carbon source for the electrocatalyst support. Herein, we report the simple fabrication and in-depth characterization of electrocatalysts using lignin-derived activated char. The activated char (LAC) was functionalized with metal phthalocyanine (FePc and MnPc) via atmosphere-controlled pyrolysis to produce monometallic M-N-Cs (L_Mn and L_Fe) and bimetallic M1-M2-N-Cs (L_FeMn) electrocatalysts. Raman spectroscopy and transmission electron microscopy (TEM) revealed a defect-rich architecture. XPS confirmed the coexistence of various nitrogen-containing active moieties. L_Fe and L_FeMn demonstrated appreciable ORR in both acidic and alkaline conditions whereas L_FeMn helped in restricting the peroxide yield, particularly in alkaline media. L_Fe and L_FeMn demonstrated remarkable onset potential (Eonset) of ∼0.942 V (vs RHE) with an E1/2 of 0.874 V (vs RHE) in 0.1 M KOH. In acid, L_FeMn had an Eonset of 0.817 V (vs RHE) and an E1/2 of ∼0.76 V (vs RHE). Finally, the L_FeMn as a cathode electrocatalyst was integrated and tested in PEMFC and AEMFC. AEMFC demonstrated optimistic performance with a peak power density of 261 mW cm−2 at the current density of ∼577 mA cm−2.

Lithium metal batteries (LMBs) will be a breakthrough in automotive applications, but they require the development of next-generation solid-state electrolytes (SSEs) to stabilize the anode interface. Polymer-in-ceramic PEO/TiO

The development of hybrid nanoscintillators is hunted for the implementation of modern detection technologies, like in high energy physics, homeland security, radioactive gas sensing, and medical imaging, as well as of the established therapies in radiation oncology, such as in X-ray activated photodynamic therapy. Engineering of the physico-chemical properties of nanoparticles (NPs) enables the manufacture of hybrids in which the conjugation of inorganic/organic components leads to increased multifunctionality and performance. However, the optimization of the properties of nanoparticles in combination with the use of ionizing radiation is not trivial: a complete knowledge on the structure, composition, physico-chemical features, and scintillation property relationships in hybrid nanomaterials is pivotal for any applications exploiting X-rays. In this paper, the design of hybrid nanoscintillators based on ZnO grown onto porous SiO

Agates from Yozgat province are appreciated on the gem market for their white and purple-blue banded colours. In this study, we present a detailed investigation aimed at the identification of the atomic and structural origin of this peculiar colouration of chalcedony. X-ray diffraction and Raman spectroscopy revealed the presence of fine grains of quartz and moganite with a preferential accumulation of the latter in the blue bands. Near-infrared diffuse absorption spectra show overtones of hydroxyls vibrations at 1425, 1900, and 2250 nm. In the visible, the broad absorption at about 500 nm, as well as its behaviour at low temperatures, is compatible with the optical activity of iron impurities in quartz matrices, such as that observed in amethysts. Peak intensities and shapes are very similar for spectra collected in blue and white bands. Accordingly, trace-element composition from laser ablation inductively coupled mass spectrometry confirmed that the two regions have similar Fe content. The perceived changes in band colours are indeed originated by differences in microstructural arrangement and size of the grains visualised through scanning electron microscopy. White and blue stripes have grains of about 5 µm and 300 nm in size, respectively, resulting in an accentuated scattering component for the white bands. Therefore, the unique purple-blue shades typical of Yozgat agates are a combination of iron-related colour centres and scattering effect.

The influence of Al2O3 as an additive and the heat-treatment regime on the luminescence spectra of gallate glass-ceramics was investigated. It is shown that its luminescence efficiency can be enhanced by changing the submicron-inhomogeneous structure of the initial glasses.

Water-in-salt solutions, i.e. solutions in which the amount of salt by volume or weight is larger than that of the solvent, are attracting increasing attention in electrochemistry due to their distinct features that often include decomposition potentials much higher than those of lower concentration solutions. Despite the high solubility of potassium acetate (KAC) in water at room temperature (up to 25 moles of salt per kg of solvent), the low cost, and the large availability, the use of highly concentrated KAC solutions is still limited to a few examples in energy storage applications and a systematic study of their physical-chemical properties is lacking. To fill this gap, we have investigated the thermal, rheological, electrical, electrochemical, and spectroscopic features of KAC/water solutions in the compositional range between 1 and 25 mol kg-1. We show the presence of a transition between the "salt-in-solvent" and "solvent-in-salt" regimes in the range of 10-15 mol kg-1. Among the explored compositions, the highest concentrations (20 and 25 mol kg-1) exhibit good room temperature conductivity values (55.6 and 31 mS cm-1, respectively) and a large electrochemical potential window (above 2.5 V).

Tailoring the precise construction of non-precious metals and carbon-based heterogeneous catalysts for electrochemical oxygen evolution reaction (OER) and methanol oxidation reaction (MOR) is crucial for energy conversion applications. Herein, this work reports the composite of Ni doped Fe2 O3 (Ni-Fe2 O3 ) with mildly oxidized multi-walled CNT (O-CNT) as an outstanding Mott-Schottky catalyst for OER and MOR. O-CNT acts as a co-catalyst which effectively regulates the charge transfer in Ni-Fe2 O3 and thus enhances the electrocatalytic performance. Ni-Fe2 O3 /O-CNT exhibits a low onset potential of 260 mV and overpotential 310 mV @ 10 mA cm-2 for oxygen evolution. Being a Mott-Schottky catalyst, it achieves the higher flat band potential of -1.15 V with the carrier density of 0.173×1024 cm-3 . Further, in presence of 1 M CH3 OH, it delivers the MOR current density of 10 mA cm-2 at 1.46 V vs. RHE. The excellent electrocatalytic OER and MOR activity of Ni-Fe2 O3 /O-CNT could be attributed to the synergistic interaction between Ni-doped Fe2 O3 and O-CNT.

In this study, we report the experimental findings of a multi-methodological and comparative investigation of a natural (from the Wah Wah Mountains of Beaver County, Utah) and three synthetic (hydrothermally grown) gem-quality red beryls by means of: gemmological standard testing, laser ablation inductively coupled mass spectroscopy, infrared and Raman spectroscopy, ultraviolet–visible–near infrared absorption spectroscopy, and single-crystal X-ray diffraction. Gemmological, crystallo-chemical, and spectroscopic features of the natural and synthetic stones enabled us to unveil the causes of their color (from red, to purplish-red, or orange-red) and how different and complementary techniques can be efficiently used to discriminate between natural and synthetic materials, based on non-destructive, micro-destructive, and destructive techniques.

Ilmenite, general formula FeTiO3, has been proposed as possible conversion anode material for lithium- and sodium-ion batteries, with theoretical capacity of 530 mAhg−1. Experimentally, the observed specific capacity for pristine ilmenite is far away from the theoretical value; for this reason, the control of morphology via alkaline hydrothermal treatment has been proposed as possible strategy to improve the electrochemical performance. At the same time FeTiO3 is prone to react with sodium and potassium hydroxide, as already demonstrated by studies on the degradation of ilmenite for the extraction of TiO2. In this paper we demonstrate that the alkaline treatment does not induce a morphological modification of the FeTiO3 powders but involved the degradation of the precursor material with the formation of different phases. A complete physicochemical and electrochemical characterization is performed with the aim of correlating structural and functional properties of the obtained products.

In this study, we report the experimental findings of a multi-methodological and comparative investigation of a natural (from the Wah Wah Mountains of Beaver County, Utah) and three synthetic (hydrothermally grown) gem-quality red beryls by means of: gemmological standard testing, laser ablation inductively coupled mass spectroscopy, infrared and Raman spectroscopy, ultraviolet–visible–near infrared absorption spectroscopy, and single-crystal X-ray diffraction. Gemmological, crystallo-chemical, and spectroscopic features of the natural and synthetic stones enabled us to unveil the causes of their color (from red, to purplish-red, or orange-red) and how different and complementary techniques can be efficiently used to discriminate between natural and synthetic materials, based on non-destructive, micro-destructive, and destructive techniques.

Mass generation of scrap tires presents a major challenge for environmental safety, however, their upcycling into carbon-based nanomaterials by the virtue of pyrolysis treatments can open up new windows for energy conversion and storage technologies in the context of the circular economy. Herein, we report the synthesis of Fe-N-C oxygen reduction reaction (ORR) electrocatalyst for fuel cell (FC) applications using carbonaceous char derived from scrap tires through microwave-assisted pyrolysis (MAP). The char obtained from MAP was activated with potassium hydroxide and then pyrolyzed at a high temperature to fabricate Fe-N-C after mixing with iron and nitrogen precursors. Finally, the developed Fe-N-C was ball-milled and acid-etched for homogenization and leaching of iron oxide nanoparticles. In this study, structural evaluation during each synthesis step was elucidated and correlated with the ORR activity in all three pHs i.e. acidic, neutral, and alkaline. Moreover, the effect of electrocatalyst loading on ORR kinetics was also analyzed using two different loadings (0.2 and 0.6 mg cm−2) on the rotating ring disk electrode (RRDE). The developed Fe-N-C demonstrated encouraging onset potentials of 0.881, 0.822, and 0.936 V vs RHE in acidic, neutral, and alkaline conditions, respectively. Whereas the ORR activity was slightly reduced after the milling-etching step. Lower peroxide yield together with a tetra-electronic reduction of oxygen was witnessed in acidic and neutral conditions, however, peroxide production was increased in the alkaline medium.

The development of hybrid nanoscintillators is hunted for the implementation of modern detection technologies, like in high energy physics, homeland security, radioactive gas sensing, and medical imaging, as well as of the established therapies in radiation oncology, such as in X-ray activated photodynamic therapy. Engineering of the physico-chemical properties of nanoparticles (NPs) enables the manufacture of hybrids in which the conjugation of inorganic/organic components leads to increased multifunctionality and performance. However, the optimization of the properties of nanoparticles in combination with the use of ionizing radiation is not trivial: a complete knowledge on the structure, composition, physico-chemical features, and scintillation property relationships in hybrid nanomaterials is pivotal for any applications exploiting X-rays. In this paper, the design of hybrid nanoscintillators based on ZnO grown onto porous SiO2 substrates (ZnO/SiO2) has been performed in the view to create nanosystems potentially suitable in X-ray activated photodynamic therapy. Indeed, cytotoxic porphyrin dyes with increasing concentrations have been anchored on ZnO/SiO2 nanoparticles through amino-silane moieties. Chemical and structural analyses correlated with photoluminescence reveal that radiative energy transfer between ZnO and porphyrins is the principal mechanism prompting the excitation of photosensitizers. The use of soft X-ray excitation results in a further sensitization of the porphyrin emission, due to augmented energy deposition promoted by ZnO in the surroundings of the chemically bound porphyrin. This finding unveils the cruciality of the design of hybrid nanoparticles in ruling the efficacy of the interaction between ionizing radiation and inorganic/organic moieties, and thus of the final nanomaterial performances towards the foreseen application.

Lithium metal batteries (LMBs) will be a breakthrough in automotive applications, but they require the development of next-generation solid-state electrolytes (SSEs) to stabilize the anode interface. Polymer-in-ceramic PEO/TiO2 nanocomposite SSEs show outstanding properties, allowing unprecedented LMBs durability and self-healing capabilities. However, the mechanism underlying the inhibition/delay of dendrite growth is not well understood. In fact, the inorganic phase could act as both a chemical and a mechanical barrier to dendrite propagation. Combining advanced in situ and ex situ experimental techniques, we demonstrate that oligo(ethylene oxide)-capped TiO2, although chemically inert toward lithium metal, imparts SSE with mechanical and dynamical properties particularly favorable for application. The self-healing characteristics are due to the interplay between mechanical robustness and high local polymer mobility which promotes the disruption of the electric continuity of the lithium dendrites (razor effect).

Following the core theme of a circular economy, a novel strategy to upcycle cigarette butt waste into platinum group metal (PGM)-free metal nitrogen carbon (M-N-C) electrocatalysts for oxygen reduction reaction (ORR) is presented. The experimental route was composed of (i) the transformation of the powdered cigarette butts into carbonaceous char via pyrolysis at 450 °C, 600 °C, 750 °C and 900 °C, (ii) the porosity activation with KOH and (iii) the functionalization of the activated chars with iron (II) phthalocyanine (FePc). The electrochemical outcomes obtained by the rotating disk electrode (RRDE) technique revealed that the sample pyrolyzed at 450 °C (i.e., cig_450) outperformed the other counterparts with its highest onset (Eon) and half-wave potentials (E1/2) and demonstrated nearly tetra-electronic ORR in acidic, neutral and alkaline electrolytes, all resulting from the optimal surface chemistry and textural properties.

We report on design and fabrication of Ni 2+ -doped glass-ceramics from a low-alkali optical glass in Li 2 O-Na 2 O-Ga 2 O 3 -SiO 2 -GeO 2 system by melting technique and subsequent thermally controlled nano-crystallization. The analysis of differential scanning calorimetry, X-ray diffraction, transmission electron microscopy, absorption and fluorescence spectroscopy reveals, for the first time, the real possibility of optimizing the integrated intensity of Ni 2+ near-infrared emission through controlled pre-treatments at temperatures of nanophase nucleation, with the enhancement up to a factor of four with respect to gallium germanosilicate glass-ceramics obtained without pre-treatments. Importantly, the effects on the light emission are shown to be related to the influence of pre-treatment on size and size distribution of the gallium oxide nanocrystals which result from subsequent crystallization at higher temperature.

A multidisciplinary non-destructive study has been carried out on historical pipe organ fragments, trying to infer whether the spatial occurrence of different crystallographic phases (that is alpha-tin, beta-tin, cassiterite or romarchite) reflects the visible alterations patterns. We could indeed derive the presence of the beta-tin phase. Several tin oxide phases have been detected too, associated with the visible occurrence of “grey regions” and hole borders (mapped by Raman spectroscopy), and hydrate phases (mapped by neutron imaging). We aim to demonstrate that neutron and Raman techniques can give relevant indications in archaeometallurgy studies of cultural heritage artifacts, where only non-destructive experiments can be performed. The combination of the two probes could be considered a protocol to be applied in the characterization of tin based specimens.

The demand for new responsive materials is continuously growing in several areas as a result of approaching the physical limits of technologies, which now calls for a drastic change of strategy. Here, we report on memory responsive oxide-in-oxide nanostructured films obtained by radio-frequency sputtering of a 7.5Li2O–2.5Na2O–20Ga2O3–45GeO2–25SiO2 (mol%) glass target produced by melt quenching. Atomic force microscopy and scanning electron microscopy show that as-deposited oxide layers exhibit native nanophase separation, with the occurrence of Ga-rich oxide nanostructures – about 15 nm thick and 100 nm in diameter – incorporated in oxide layers about 70 nm thick. Interestingly, despite the wide band gap (above 4 eV), the nanostructured oxide films reveal the formation of unconventional electric field dependent charge transport paths across the material. The frequency and temperature dependence of electric conductivity and dielectric function highlights n-type conduction sustained by charge percolation through the oxide layer. Importantly, the results demonstrate the occurrence of conductivity changes by more than an order of magnitude in a few volts, and trapped charge values up to 1016 electrons per cm3.

The influence of fiber drawing on mechanical and vibrational properties of RE-doped sol-gel silica is disclosed by a comparison of bulk silica, before and after the melting process, and fibers. The mechanical characterization is carried out by nanoindentation technique: hardness and elastic modulus are found to be consistent with those of Corning 7980 reference glass, and related to the elasto-plastic behavior of the glassy material. Our results evidence an increase of the resistance of fibers to fracture under an applied load, ascribed to drawing-induced residual stresses. Their impact on sol-gel silica mechanical properties is further disclosed by complementary vibrational characterization by Raman and FTIR spectroscopies, confirming the occurrence of a modification of the structural features after the drawing process and of residual stresses in the fibers. The overall results highlight the role of the fiber drawing in improving the glass mechanical properties, causing a slight rearrangement of the silica structure.

We present a completely non-destructive approach to analyse a set of historical glass mosaic tesserae. Aim of the study is to obtain a qualitative and quantitative characterization of the glass matrix in terms of elements and mineralogical phases. Several non-destructive techniques have been applied like Particle-Induced X-ray Emission, Particle-Induced Gamma-ray Emission, micro-Raman spectroscopy, neutron resonance capture analysis and neutron activation analysis in order to combine different technique strengths and to explore the effect of different range sizes for the analysis. Yet, best practices require the use of combined analysis and different skills. The paradigm of a non-destructive multi-analytical approach is suggested for a comprehensive investigation in non-homogeneous real samples, like historical glass mosaic tesserae.

A novel route for the valorization of waste into valuable products was developed. Surgical masks commonly used for COVID 19 protection by stopping aerosol and droplets have been widely used, and their disposal is critical and often not properly pursued. This work intended to transform surgical masks into platinum group metal-free electrocatalysts for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) as well as into crude oil. Surgical masks were subjected to controlled-temperature and -atmosphere pyrolysis, and the produced char was then converted into electrocatalysts by functionalizing it with metal phthalocyanine of interest. The electrocatalytic performance characterization towards ORR and HER was carried out highlighting promising activity. At different temperatures, condensable oil fractions were acquired and thoroughly analyzed. Transformation of waste surgical masks into electrocatalysts and crude oil can open new routes for the conversion of waste into valuable products within the core of the circular economy.

Ionic liquids (ILs) are an increasingly important component of electrolytes for lithium and sodium batteries. Here, the physicochemical properties of the system N-propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr13TFSI) ionic liquid and NaTFSI are investigated vs. the concentration of the sodium salt and the temperature. The explored concentration range was (1-x) Pyr13TFSI: x NaTFSI with x (mole fraction) = 0, 0.02, 0.05, 0.1, 0.2. 23Na solid-state NMR reveals that the Na+ ions exist in two distinct environments: mobile Na+ ions (1), and Na+ ions involved in clusters or even bigger interacting networks (2). The ratio between mobile and bonded Na+ populations increases with temperature and decreases with increasing salt concentration, reaching 100% at 60 °C for the most diluted compositions. Raman spectroscopy allows to identify the quantity of free and bonded anions depending on the concentration, and to measure the number of Na+ ions solvating the TFSI− anion (SN = 4). The combined NMR and Raman results allow us to estimate the salt solubility range, x = 0.12 ± 0.02. The composition x = 0.1 showed satisfying stability when cycled versus high-potential cathodic material Na0.44MnO2 (NMO) in a cell Na/IL/NMO.

Water in salt solutions are a new class of electrolytes developed with the aim of increasing the electrochemical stability of aqueous electrolytes without decreasing the transport properties. Among them, aqueous solutions of potassium acetate (CH3COOK, AcK) have received little attention, despite its large solubility in water at room temperature (25 mol kg−1) and the very low cost. With the idea of developing cost-effective and good performing Electrochemical Double Layer Capacitors (EDLCs), a symmetric device based on a low-cost coal derived carbon (F400) and highly concentrated AcK solutions as electrodes and electrolytes, respectively, was fabricated and optimized. The best results are obtained with the system F400/20 mol kg−1 AcK/F400 able to deliver a gravimetric energy density of 26 Wh kg−1 at an average power of 1.4 kW kg−1.

KLuS2 single crystal samples undoped and doped with a low (5 %) or high (38 %) concentration of trivalent thulium or ytterbium ions were synthesized in the form of thin hexagonal plates. The low phonon energy ( ∼ 220 cm−1) was confirmed using Raman spectroscopy. Samples were studied also by using optical absorption and emission as well as electron paramagnetic resonance spectroscopy and the observed spectral features are discussed. In particular, the 5 % Yb doped samples demonstrate homogeneous dopant distribution inside the material over the lutetium sites. No other signals either from potassium site or the exchange coupled ions were detected. For infrared transitions the luminescence kinetic was determined. Significantly broad infrared emission bands (at 1.4, 1.8 and 2.3 μm for Tm3+, 1 μm for Yb3+) and long decay times (e.g. 0.4 ms from 3H4 to 19 ms from 3F4 levels of Tm3+, 1.4 ms from 2F5/2 level of Yb3+) make those materials perspective for future laser development.

Gallium incorporation in silicate glasses gives rise to compounds in which the nucleation and growth of Ga-oxide nanostructures can be designer controlled so as to obtain a number of functional properties for photonic applications. However, despite planar geometry pertains to a large part of modern technology, no information is available yet on the scalability of Ga-oxide segregation mechanisms in oxide thin films. In fact, incorporated Ga-oxide nanostructures have only been obtained in bulk materials. Here we show that deposition of Ga-alkali-germanosilicate thin films by radiofrequency-plasma sputtering gives rise to Ga-oxide nanostructures incorporated in an amorphous matrix. X-ray diffraction, X-ray reflectivity, small-angle X-ray scattering, and atomic force microscopy data unveil the formation of lenticular nanoaggregates, only a few nm thick, even in as-deposited materials as a result of two-dimensional aggregation of spinel-like Ga2O3 nanoparticles. Importantly, the aggregate size distribution is controlled not only by the temperature but also by the film thickness when it is reduced from 102 nm to only a few nm. The results open the way to the design of oxide-in-oxide thin films with incorporated networks of nanostructures which can act as percolation paths for unconventional electric responses in neuromorphic functional systems.

Defect engineering operated on metal oxides by chemical and structural modifications may strongly affect properties suitable for various applications such as photoelectrochemical behavior, charge transport, and luminescence. In this work, we report the tunable optical features observed in undoped monoclinic HfO2 nanocrystals and their dependence on the structural properties of the material at the nanoscale. Transmission electron microscopy together with X-ray diffraction and surface area measurements were used to determine the fine structural modifications, in terms of crystal growth and coalescence of crystalline domains, occurring during a calcination process in the temperature range from 400 to 1000 °C. The fit of the broad optical emission into spectral components, together with time-resolved photoluminescence, allowed us to identify the dual nature of the emission at 2.5 eV, where an ultrafast defect-related intrinsic luminescence (with a decay time of a few nanoseconds) overlaps with a slower emission (decay of several microseconds) due to extrinsic Ti-impurity centers. Moreover, the evolution of intrinsic visible bands during the material transformation was monitored. The relationship between structural parameters uniquely occurring in nanosized materials and the optical properties was investigated and tentatively modeled. The blue emissions at 2.5 and 2.9 eV are clearly related to defects lying at crystal boundaries, while an unprecedented emission at 2.1 eV enables, at relatively low calcination temperatures, the white luminescence of HfO2 under near-UV excitation.

Two bacterial strains, Achromobacter sp. (ACH01) and Sphingomonas sp. (SPH01), were isolated from a heavily polycyclic aromatic hydrocarbon (PAH)-contaminated soil (5431.3 ± 102.3 ppm) for their capacity to use a mixture of anthracene, pyrene, phenanthrene and fluorene as sole carbon sources for growth and for the capacity to produce biosurfactants. The two strains were exploited for bioaugmentation in a biopile pilot plant to increase the bioavailability and the degradation of the residual PAH contamination (99.5 ± 7.1 ppm) reached after 9 months of treatment. The denaturing gel gradient electrophoresis (DGGE) profile of the microbial ecology of the soil during the experimentation showed that the bioaugmentation approach was successful in terms of permanence of the two strains in the soil in treatment. The bioaugmentation of the two bacterial isolates positively correlated with the PAH depletion that reached 7.9 ± 2 ppm value in 2 months of treatment. The PAH depletion was assessed by the loss of the phyto-genotoxicity of soil elutriates on the model plant Vicia faba L., toxicological assessment adopted also to determine the minimum length of the decontamination process for obtaining both the depletion of the PAH contamination and the detoxification of the soil at the end of the process. The intermediate phases of the bioremediation process were the most significant in terms of toxicity, inducing genotoxic effects and selective DNA fragmentation in the stem cell niche of the root tip. The selective DNA fragmentation can be related to the selective induction of cell death of mutant stem cells that can compromise offsprings.

The knowledge advancement in the physics of silicon dioxide has promoted ground-breaking progress, from microelectronics to fibre optics. However, the SiO2 exciton decay mechanism is still mostly unrevealed. Here, we analyse the temperature dependence of interband-excited luminescence and the reflectivity by means of synchrotron radiation on a wide selection of SiO2 materials. This enables us to decouple the band-to-band recombination steps from non-radiative decay pathways that typically mask the relaxation mechanisms. We show that band-to-band excitations decay into two competitive correlated channels leading to green and red luminescence so far ascribed to independent transitions. Here we discuss the assignment to a dual relaxation route involving either ‘free’ or ‘interacting’ non-bridging-oxygen sites. Such an interpretation suggests an explanation for the elusive non-bridging-oxygen centres in quartz. The reflectivity spectra finally demonstrates a general relationship between exciton spectral position and bandwidth in SiO2 and clarifies the role of disorder in exciton localization. Silicon dioxide is a crucial material in the world of photonics but aspects of its optical decay mechanisms are still not fully understood. The authors use synchrotron radiation to analyse emission processes for different types of silica and quartz and deduce by what mechanisms they may occur.

Nanocrystals (NCs) surface characterization is a fundamental step for understanding the physical and chemical phenomena involved at the nanoscale. Surface energy and chemistry depend on particle size and composition, and, in turn, determine the interaction of NCs with the surrounding environment, their properties and stability, and the feasibility of nanocomposites. This work aims at extracting more information on the surface of different titanium dioxide polymorphs using

During the last decades many studies have been carried out to investigate how point defects and aggregates respond and evolve in natural Type Ia diamonds as a result of treatments, and a number of underlying mechanisms have been identified and interpreted. However, the analysis of radiation-induced creation/ionization of defects, as well as their migration and aggregation in secondary defect structures, often requires experimental approaches which can hardly constitute a simple-to-use diagnostic tool for the identification of artificially treated diamonds. Here we disclose a novel simple indicator of artificial exposure of Type Ia diamonds to ionizing radiations and subsequent annealing. This indicator consists in narrow photoluminescence lines in the red region, between 681 and 725 nm, we recently found to result from vacancies trapped by interstitial carbon aggregates and platelets. Our results demonstrate that interstitial structures become sites of vacancy trapping – by thermal migration of radiation-induced vacancies – only when diamond undergoes treatments. We give the rigorous validation of the new spectroscopic probe of artificial treatments analysing photoluminescence and infrared absorption spectra of well-known H1b and H1c centres in a hundred samples. Importantly, the method is based on emission lines which do not require neither high photon-energy excitation nor cryogenic temperatures.

Optical properties of yttria-aluminoborate (YAB) glasses with general composition 10(CexTbyY(1-x-y))-30Al2O3-60B2O3 are investigated and compared with data available on YAB crystals with huntite-like structure. Ce doped samples show optical features ascribable to preferential location of rare earth ions in sites with specific geometry similar to that observed in crystalline structures. Samples prepared with Tb ions as emission activator and Ce ions as sensitizer have been studied within the framework of non-radiative energy transfer. The resulting Forster radius is of 4.6 ± 0.5 A comparable with that observed in Ce/Tb co-doped YAl3(BO3)4 crystals. The investigated materials possess radio- and photoluminescence emission efficiencies and performances comparable to that of crystalline counterparts with the advantage of having easiness of preparation and workability typical of glassy systems.

Nanocrystals (NCs) surface characterization is a fundamental step for understanding the physical and chemical phenomena involved at the nanoscale. Surface energy and chemistry depend on particle size and composition, and, in turn, determine the interaction of NCs with the surrounding environment, their properties and stability, and the feasibility of nanocomposites. This work aims at extracting more information on the surface of different titanium dioxide polymorphs using1H-TD-NMR of water. Taking advantage of the interaction between water molecules and titanium dioxide NCs, it is possible to correlate the proton transverse relaxation times (T2) as the function of the concentration and the specific surface area (δp·Cm) and use it as an indicator of the crystal phase. Examples of three different crystals phase, rutile, anatase, and brookite, have been finely characterized and their behavior in water solution have been studied with TD-NMR. The results show a linear correlation between relaxivity (R2) and their concentration Cm. The resulting slopes, after normalization for the specific surface, represent the surface/water interaction and range from 1.28 g m-2s-1of 50 nm rutile nanocrystals to 0.52 for similar sized brookite. Even higher slopes (1.85) characterize smaller rutile NCs, in qualitative accordance with the trends of surface energy. Thanks to proton relaxation phenomena that occur at the NCs surface, it is possible to differentiate the crystal phase and the specific surface area of titanium dioxide polymorphs in water solution.

The development of cheap and reliable time-temperature indicators (TTIs) can greatly improve customer satisfaction with respect to the correct handling and storage of perishable goods. A series of new irreversible thermochromic squaraine dyes enables the preparation of simple TTIs whose time-temperature regime can be controlled by selection of the appropriate molecule/substrate combinations.

In this Letter, we present detailed absorption and emission data on nanostructured germanosilicate glasses and glass ceramics containing Ga2O3 nanophases and doped with Gd ions. The results show that these systems are suitable hosts for the enhancement of the excitation cross section of rare earth ions via energy transfer from the gallium oxide nanophase with a related quantum yield of 21%. The role of matrix composition and nanostructure morphology on the Gd emission is discussed.

Ternary CuInS