Search

In the present study, LiFePO4/CNF self-standing cathodes for LIBs are synthesized by electrospinning. A lower active material amount (12.3 and 34.5 wt%) is used, compared to the conventional tape-casted cathodes (70–85 wt%). The characterization techniques (XRPD, SEM, TEM, EDS, Raman spectroscopy, and thermogravimetry) confirm that the olivine-type structure of LiFePO4 is maintained in the binder-free electrodes, and the active material is homogeneously dispersed into and within the carbon nanofibers. The electrochemical investigation demonstrates that higher Li+ diffusion coefficients (1.36 × 10−11 cm2/s) and improved reversibility are reached for free-standing electrodes, compared to the LiFePO4 tape-casted cathode (80 wt% of active material) appositely prepared for comparison. The 34.5 wt% LiFePO4 self-standing cathode displays a lower capacity fading, good reversibility and stability, enhanced capacity values at C-rates higher than 5C, and a good lifespan when cycled 1000 cycles at 1C and further cycled up to 20C, compared to the tape-casted counterpart. Notably, the improved electrochemical performances are obtained by only the 34.5 wt% of active material. The results evidence the relevant role of the CNF matrix suitable to host LiFePO4, to promote electrolyte permeation and contact with the active material, and to increase the electronic conductivity.

Convenient, rapid, highly sensitive and on-site iron determination is important for environmental safety and human health. We developed a sensing system for the detection of Fe(III) in water based on 7-mercapto-4-methylcoumarine (MMC)-stabilized silver-coated gold nanostars (GNS@Ag@MMC), exploiting a redox reaction between the Fe(III) cation and the silver shell of the nanoparticles, which causes a severe transformation of the nanomaterial structure, reverting it to pristine GNSs. This system works by simultaneously monitoring changes in the Localized Surface Plasmon Resonance (LSPR) and Surface-Enhanced Raman Spectroscopy (SERS) spectra as a function of added Fe(III). The proposed sensing system is able to detect the Fe(III) cation in the 1.0 × 10−5–1.5 × 10−4 M range, and its selectivity of the GNS@Ag@MMC sensor toward iron has been verified monitoring the LSPR and the SERS response to other cations with a clear selectivity toward Fe(III).

Aluminum garnets display exceptional adaptability in incorporating mismatching elements, thereby facilitating the synthesis of novel materials with tailored properties. This study explored Ce3+-doped Tb3Al5−xScxO12 crystals (where x ranges from 0.5 to 3.0), revealing a novel approach to control luminescence and photoconversion through atomic size mismatch engineering. Raman spectroscopy confirmed the coexistence of garnet and perovskite phases, with Sc substitution significantly influencing the garnet lattice and induced A1g mode softening up to Sc concentration x = 2.0. The Sc atoms controlled sub-eutectic inclusion formation, creating efficient light scattering centers and unveiling a compositional threshold for octahedral site saturation. This modulation enabled the control of energy transfer dynamics between Ce3+ and Tb3+ ions, enhancing luminescence and mitigating quenching. The Sc admixing process regulated luminous efficacy (LE), color rendering index (CRI), and correlated color temperature (CCT), with adjustments in CRI from 68 to 84 and CCT from 3545 K to 12,958 K. The Ce3+-doped Tb3Al5−xScxO12 crystal (where x = 2.0) achieved the highest LE of 114.6 lm/W and emitted light at a CCT of 4942 K, similar to daylight white. This approach enables the design and development of functional materials with tailored optical properties applicable to lighting technology, persistent phosphors, scintillators, and storage phosphors.

Self-standing Na3MnTi(PO4)3/carbon nanofiber (CNF) electrodes are successfully synthesized by electrospinning. A pre-synthesized Na3MnTi(PO4)3 is dispersed in a polymeric solution, and the electrospun product is heat-treated at 750 °C in nitrogen flow to obtain active material/CNF electrodes. The active material loading is 10 wt%. SEM, TEM, and EDS analyses demonstrate that the Na3MnTi(PO4)3 particles are homogeneously spread into and within CNFs. The loaded Na3MnTi(PO4)3 displays the NASICON structure; compared to the pre-synthesized material, the higher sintering temperature (750 °C) used to obtain conductive CNFs leads to cell shrinkage along the a axis. The electrochemical performances are appealing compared to a tape-casted electrode appositely prepared. The self-standing electrode displays an initial discharge capacity of 124.38 mAh/g at 0.05C, completely recovered after cycling at an increasing C-rate and a coulombic efficiency ≥98%. The capacity value at 20C is 77.60 mAh/g, and the self-standing electrode exhibits good cycling performance and a capacity retention of 59.6% after 1000 cycles at 1C. Specific capacities of 33.6, 22.6, and 17.3 mAh/g are obtained by further cycling at 5C, 10C, and 20C, and the initial capacity is completely recovered after 1350 cycles. The promising capacity values and cycling performance are due to the easy electrolyte diffusion and contact with the active material, offered by the porous nature of non-woven nanofibers.

GeFe2O4 (GFO) is a germanium mineral whose spinel crystal structure determines its interesting functional properties. Recently, it was proposed for application as an anode for Sodium and Lithium-Ion Batteries (SIBs and LIBs) thanks to its combined conversion and alloying electrochemical mechanism. However, its entire potential is limited by the poor electronic conductivity and volumetric expansion during cycling. In the present paper, pure and Sn or Mg doped GFO samples obtained from mechano-chemical solid-state synthesis and properly carbon coated were structurally and electrochemically characterized and proposed, for the first time, as anodes for SIBs. The spinel cubic structure of pure GFO is maintained in doped samples. The expected redox processes, involving Fe and Ge ions, are evidenced in the electrochemical tests. The Sn doping demonstrated a beneficial effect on the long-term cycling (providing 150 mAh/g at 0.2 C after 120 cycles) and on the capacity values (346 mAh/g at 0.2 C with respect to 300 mAh/g of the pure one), while the Mg substitution was less effective.

Scientific and industrial reasons dictate the study of the solid state of imepitoin, a highly safe and tolerable anticonvulsant drug used in the therapy of epileptic dogs that was approved in the Europe Union in 2013. Our investigations allowed us to discover the existence of a new polymorph of imepitoin, which finds itself in a monotropic relationship with the crystalline form (polymorph I) already known and present on the market. This form (polymorph II), obtained by crystallization from xylene, remains metastable under ambient conditions for at least 1 year. Both solid forms were characterized by thermal (DSC and TGA), spectroscopic (FT-IR and Raman), microscopic (SEM and HSM), and diffractometric techniques. The thermodynamic relationship between the two polymorphs (monotropic) is such that it is not possible to study the melting of polymorph II, not even by adopting appropriate experimental strategies. Our measurements highlighted that the melting peak of imepitoin actually also includes an onset of melt decomposition. The ab initio structure solution, obtained from synchrotron X-ray powder diffraction data collected at room temperature, allowed us to determine the crystal structure of the new polymorph (II). It crystallizes in the monoclinic crystal structure, P21/c space group (#14), with a = 14.8687(6) Å, b = 7.2434(2) Å, c = 12.5592(4) Å, β = 107.5586(8)°, V = 1289.61(8) Å3, and Z = 4.

The NASICON-structured Na3MnZr(PO4)3 compound is a promising high-voltage cathode material for sodium-ion batteries (SIBs). In this study, an easy and scalable electrospinning approach was used to synthesize self-standing cathodes based on Na3MnZr(PO4)3 loaded into carbon nanofibers (CNFs). Different strategies were applied to load the active material. All the employed characterization techniques (X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), thermal gravimetric analysis (TGA), and Raman spectroscopy) confirmed the successful loading. Compared to an appositely prepared tape-cast electrode, Na3MnZr(PO4)3/CNF self-standing cathodes demonstrated an enhanced specific capacity, especially at high C-rates, thanks to the porous conducive carbon nanofiber matrix. Among the strategies applied to load Na3MnZr(PO4)3 into the CNFs, the electrospinning (vertical setting) of the polymeric solution containing pre-synthesized Na3MnZr(PO4)3 powders resulted effective in obtaining the quantitative loading of the active material and a homogeneous distribution through the sheet thickness. Notably, Na3MnZr(PO4)3 aggregates connected to the CNFs, covered their surface, and were also embedded, as demonstrated by TEM and EDS. Compared to the self-standing cathodes prepared with the horizontal setting or dip–drop coating methods, the vertical binder-free electrode exhibited the highest capacity values of 78.2, 55.7, 38.8, 22.2, 16.2, 12.8, 10.3, 9.0, and 8.5 mAh/g at C-rates of 0.05C, 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C, and 20C, respectively, with complete capacity retention at the end of the measurements. It also exhibited a good cycling life, compared to its tape-cast counterpart: it displayed higher capacity retention at 0.2C and 1C, and, after cycling 1000 cycles at 1C, it could be further cycled at 5C, 10C, and 20C.

Handly and easy-to-use optical instrumentation is very important for food safety monitoring, as it provides the possibility to assess law and health compliances at every stage of the food chain. In particular, the Surface-enhanced Raman Scattering (SERS) method appears highly promising because the intrinsic drawback of Raman spectroscopy, i.e., the natural weakness of the effect and, in turn, of the signal, is overcome thanks to the peculiar interaction between laser light and plasmonic excitations at the SERS substrate. This fact paved the way for the widespread use of SERS sensing not only for food safety but also for biomedicine, pharmaceutical process analysis, forensic science, cultural heritage and more. However, the current technological maturity of the SERS technique does not find a counterpart in the recognition of SERS as a routine method in compliance protocols. This is mainly due to the very scattered landscape of SERS substrates designed and tailored specifically for the targeted analyte. In fact, a very large variety of SERS substrates were proposed for molecular sensing in different environments and matrices. This review presents the advantages and perspectives of SERS sensing in food safety. The focus of the survey is limited to specific analytes of interest for producers, consumers and stakeholders in Oltrepò Pavese, a definite regional area that is located within the district of Pavia in the northern part of Italy. Our attention has been addressed to (i) glyphosate in rice fields, (ii) histamine in a world-famous local product (wine), (iii) tetracycline, an antibiotic often detected in waste sludges that can be dangerous, for instance in maize crops and (iv) Sudan dyes—used as adulterants—in the production of saffron and other spices, which represent niche crops for Oltrepò. The review aims to highlight the SERS performance for each analyte, with a discussion of the different methods used to prepare SERS substrates and the different reported limits of detection.

Detecting and quantifying micro- and nanoplastics (MNPs) in the environment is a crucial task that needs to be addressed as soon as possible by the scientific community. Many analytical techniques have been proposed, but a common agreement on analytical protocols and regulations still has to be reached. Nanomaterial-based techniques have shown promising results in this field. In this review, we focus on the recent results published on the use of plasmonic noble metal materials for the detection of MNPs. Plasmonic materials can be exploited in different ways due to their peculiar optical end electronic properties. Surface plasmon resonance, plasmon enhanced fluorescence, UV–Vis spectroscopy, and surface enhanced Raman scattering (SERS) will be considered in this review, examining the advantages and drawbacks of each approach.

ZnS–graphene composites (ZnSGO) were synthesized by a hydrothermal process and loaded onto carbon nanofibers (CNFs) by electrospinning (ZnS–GO/CNF), to obtain self-standing anodes for SIBs. The characterization techniques (XRPD, SEM, TEM, EDS, TGA, and Raman spectroscopy) confirm that the ZnS nanocrystals (10 nm) with sphalerite structure covered by the graphene sheets were successfully synthesized. In the ZnS–GO/CNF anodes, the active material is homogeneously dispersed in the CNFs’ matrix and the ordered carbon source mainly resides in the graphene component. Two self-standing ZnS–GO/CNF anodes (active material amount: 11.3 and 24.9 wt%) were electrochemically tested and compared to a tape-casted ZnS–GO example prepared by conventional methods (active material amount: 70 wt%). The results demonstrate improved specific capacity at high C-rate for the free-standing anodes compared to the tape-casted example (69.93 and 92.59 mAh g−1 at 5 C for 11.3 and 24.9 wt% free-standing anodes, respectively, vs. 50 mAh g−1 for tape-casted). The 24.9 wt% ZnS–GO/CNF anode gives the best cycling performances: we obtained capacities of 255–400 mAh g−1 for 200 cycles and coulombic efficiencies ≥ 99% at 0.5 C, and of 80–90 mAh g−1 for additional 50 cycles at 5 C. The results suggest that self-standing electrodes with improved electrochemical performances at high C-rates can be prepared by a feasible and simple strategy: ex situ synthesis of the active material and addition to the carbon precursor for electrospinning.

Surface-enhanced Raman scattering (SERS) is becoming widely used as an analytical tool, and the search for stable and highly responsive SERS substrates able to give ultralow detection of pollutants is a current challenge. In this paper we boosted the SERS response of Gold nanostars (GNS) demonstrating that their coating with a layer of silver having a proper thickness produces a 7-fold increase in SERS signals. Glass supported monolayers of these GNS@Ag were then prepared using simple alcoxyliane chemistry, yielding efficient and reproducible SERS chips, which were tested for the detection of molecules representative of different classes of pollutants. Among them, norfloxacin was detected down to 3 ppb, which is one of the lowest limits of detection obtained with this technique for the analyte.

Low-cost and simple methods are constantly chased in order to produce less expensive lithium-ion batteries (LIBs) while possibly increasing the energy and power density as well as the volumetric capacity in order to boost a rapid decarbonization of the transport sector. Li alloys and tin-carbon composites are promising candidates as anode materials for LIBs both in terms of capacity and cycle life. In the present paper, electrospinning was employed in the preparation of Sn/SnOx@C composites, where tin and tin oxides were homogeneously dispersed in a carbonaceous matrix of carbon nanofibers. The resulting self-standing and light electrode showed a greatly enhanced performance compared to a conventional electrode based on the same starting materials that are simply mixed to obtain a slurry then deposited on a Cu foil. Fast kinetics were achieved with more than 90% of the reaction that resulted being surface-controlled, and stable capacities of about 300 mAh/g over 500 cycles were obtained at a current density of 0.5 A/g.

Spinel phases, with unique and outstanding physical properties, are attracting a great deal of interest in many fields. In particular, MgFe2O4, a partially inverted spinel phase, could find applications in medicine thanks to the remarkable antibacterial properties attributed to the generation of reactive oxygen species. In this paper, undoped and Ag-doped MgFe2-xAgxO4 (x = 0.1 and 0.3) nanoparticles were prepared using microwave-assisted combustion and sol–gel methods. X-ray powder diffraction, with Rietveld structural refinements combined with micro-Raman spectroscopy, allowed to determine sample purity and the inversion degree of the spinel, passing from about 0.4 to 0.7 when Ag was introduced as dopant. The results are discussed in view of the antibacterial activity towards Escherichia coli and Staphylococcus aureus, representative strains of Gram-negative and Gram-positive bacteria. The sol–gel particles were more efficient towards the chosen bacteria, possibly thanks to the nanometric sizes of metallic silver, which were well distributed in the powders and in the spinel phase, with respect to microwave ones, that, however, acquired antibacterial activity after thermal treatment, probably due to the nucleation of hematite, itself displaying well-known antibacterial properties and which could synergistically act with silver and spinel.

The osseointegration of titanium implants is allowed by the TiO2 layer that covers the implants. Titania can exist in amorphous form or in three different crystalline conformations: anatase, rutile and brookite. Few studies have characterized TiO2 covering the surface of dental implants from the crystalline point of view. The aim of the present study was to characterize the evolution of the TiO2 layer following different surface treatments from a crystallographic point of view. Commercially pure titanium and Ti-6Al-4V implants subjected to different surface treatments were analyzed by Raman spectroscopy to evaluate the crystalline conformation of titania. The surface treatments evaluated were: machining, sandblasting, sandblasting and etching and sandblasting, etching and anodization. The anodizing treatment evaluated in this study allowed to obtain anatase on commercially pure titanium implants without altering the morphological characteristics of the surface.

The aim of the study was to qualitatively investigate the structure of the surface layer of TiO2 on dental implants made of Ti-6Al-4V subjected to different manufacturing treatments. M (machined), B (Al2O3-blasted), E (HNO3\HF-etched), B + E and A (B + E + anodized) implants and a further group receiving the same treatments as the first group with the addition of a final decontamination with cold plasma were included in the study. Examination was performed using micro-Raman spectroscopy. The surface treatments evaluated did not achieve the formation of crystalline TiO2. The increase in the complexity of surface treatment produced a proportional increase in the thickness of amorphous TiO2 oxide. In the B + E group, the plasma treatment enhanced the amorphous oxide thickness of TiO2. The other surfaces treated by plasma decontamination did not show a difference to the respective untreated ones. The investigated surface treatments did not change the crystalline cage of TiO2 in Ti-6Al-4V implants but affected the thickness of the oxide layer. The biological response could be influenced by different oxide thicknesses. Additional information on superficial TiO2 structural organization can be obtained by micro-Raman evaluation of dental implants. Dental implants with B + E + plasma and A superficial treatments allowed the maximum formation of the amorphous oxide thickness.

The adhesion and proliferation of bacteria on abiotic surfaces pose challenges in both health care and industrial applications. Gold nanostars (GNSs) monolayers grafted on glass have demonstrated to exert antibacterial action due to their photo-thermal features. Here, these GNS layers were further functionalized using thiols monolayers, in order to impart different wettability to the surfaces and thus adding a feature that could help to fight bacterial proliferation. Thiol that has different functional groups was used and the thiol-protected surfaces were characterized by means of UV-vis spectroscopy, contact angles, SEM and surface enhanced Raman spectroscopy (SERS). We verified that (i) coating with the proper thiol allows us to impart high hydrophilicity or hydrophobicity to the surfaces (with contact angle values ranging from 10 to 120°); (ii) GNS monolayers are strongly stabilized by functionalization with thiols, with shelf stability increasing from a few weeks to more than three months and (iii) photo-thermal features and subsequent antibacterial effects caused by hyperthermia are not changed by thiols layers, allowing us to kill at least 99.99% of representative bacterial strains.

Weakly concentrated “as-grown” and reduced SrTiO3:Mn crystals and ceramics are investigated by means of electron paramagnetic resonance (EPR) to get new insights concerning the Mn substitution in the strontium titanate structure. The temperature dependence of Mn2+ and Mn4+ EPR spectra strongly indicates the formation of MnO2 or MnO small particles to be the favored configuration for the Mn insertion in SrTiO3. Only a part of manganese ions incorporates into the crystal lattice in B position as Mn4+ ions. [ABSTRACT FROM AUTHOR]

Photoconductivity (PC), thermally stimulated conductivity (TSC), photoluminescence (PL), thermoluminescence (TL), and electron spin resonance (ESR) measurements have been made on single crystals of potassium tantalate over the temperature range 4.2-290 K. We revealed two sorts of O[SUP-] shallow hole centers which are responsible for the two temperature regions of PL and PC enhancement: T,70 K and 100-150 K. Both O[SUP-] centers were identified by their ESR spectra. While at low temperatures PL and PC have a rather intrinsic origin, i.e., they do not depend essentially on the sort or quality of crystals, at 100-150 K both quantities strongly depend on the defect content and vanish in well-oxidized crystals. We show that O[SUP-] centers serve as radiative electron-hole recombination centers. Their energy levels are situated at 0.08 and 0.16 eV above the top of the valence band. Measurements of TSC and TL after UV irradiation revealed several glow peaks at temperatures 18-30 K and 65-70 K. There is a good correlation between TSC and TL intensity in different samples as well as after annealing in O[SUB2] and H[SUB2] atmospheres. Because electrons are mobile species in KtaO[SUB3] we attribute both TSC and TL to the thermal ionization of the same shallow donor centers related with isolated oxygen vacancies. The experimental data were treated in a one-trap/one-recombination center model, which takes into account the presence of "thermally disconnected" deep electron traps. [ABSTRACT FROM AUTHOR]

Weakly concentrated 'as-grown' and reduced SrTi[O.sub.3]:Mn crystals and ceramics are examined by using electron paramagnetic resonance (EPR) to understand the Mn substitution in the strontium titanate structure. The temperature dependence of [Mn.sup.2+] and [Mn.sup.4+] EPR spectra has indicated the formation of Mn[O.sub.2] or MnO small particles to be the favored configuration for the Mn insertion in SrTi[O.sub.3].