Search Results (75)

Different sulfates (Ca-, Mg, and Fe- sulfates) have been extensively detected on the Martian surface. As one of the Martian sulfates, the presence of ferrous sulfates will provide valuable clues about the redox environment, hydrological processes, and climatic history of ancient Mars. In this study, three hydrated ferrous sulfates were prepared in the laboratory by heating dehydration reactions. These samples were analyzed using X-ray Diffraction (XRD) to confirm their phase and homogeneity. Subsequently, Raman, mid-infrared (MIR) spectra, visible near-infrared (VNIR) spectra, and laser-induced breakdown spectroscopy (LIBS) were measured and analyzed. The results demonstrate that the spectra of three hydrated ferrous sulfates exhibit distinctive features (e.g., the v₁ and v₃ features of ${\mathrm{S}\mathrm{O}}_4^{2-}$ tetrahedra in their Raman and MIR spectra) that can offer new insights for identifying different ferrous sulfates on Mars and aid in the interpretation of in-situ data collected by instruments such as the Scanning Habitable Environments with Raman & Luminescence for Organics & Chemicals (SHERLOC), SuperCam, and ChemCam, etc. Full article

Watermelons are in high demand for their juicy texture and sweetness, which is linked to their soluble solids content (SSC). Traditionally, watermelons have been sold as whole fruits. However, the decline in the mean size of households and the very large size of the fruits, together with high prices, mainly at the beginning of the season, mean that supermarkets now sell them as half fruits. For consumers, it is important to know in advance that the fruits that they are purchasing are of a high quality, based not only on external flesh colour but also on sweetness. Near-infrared spectroscopy (NIRS) and Raman spectroscopy were used for the in situ determination of SSC in half watermelons while simulating supermarket conditions. A handheld linear variable filter (LVF) device and an all-in-one (AIO) Process Raman analyser were used for the NIRS and Raman analysis, respectively. The excellent results obtained—including residual predictive deviation for prediction (RPD_p) values of 3.06 and 2.90 for NIRS and Raman, respectively—showed the viability of NIRS and Raman spectroscopies for the prediction of sweetness in half watermelons. Full article

Hybrid organic/inorganic conducting and magnetic composites of core–shell type have been prepared by in-situ coating of nickel microparticles with polypyrrole. Three series of syntheses have been made. In the first, pyrrole was oxidised with ammonium peroxydisulfate in water in the presence of various amounts of nickel and the composites contained up to 83 wt% of this metal. The second series used 0.1 M sulfuric acid as a reaction medium. Finally, the composites with polypyrrole nanotubes were prepared in water in the presence of structure-guiding methyl orange dye. The nanotubes have always been accompanied by the globular morphology. FTIR and Raman spectroscopies confirmed the formation of polypyrrole. The resistivity of composite powders of the order of tens to hundreds Ω cm was monitored as a function of pressure up to 10 MPa. The resistivity of composites slightly increased with increasing content of nickel. This apparent paradox is explained by the coating of nickel particles with polypyrrole, which prevents their contact and subsequent generation of metallic conducting pathways. Electrical properties were practically independent of the way of composite preparation or nickel content and were controlled by the polypyrrole phase. On the contrary, magnetic properties were determined exclusively by nickel content. The composites were used as a solid phase to prepare a magnetorheological fluid. The test showed better performance when compared with a different nickel system reported earlier. Full article

An in situ electron microprobe study of detrital minerals yielded important insights into the diagenetic history of the Cretaceous-to-Paleogene flysch sandstones from the Chvalčov site, Rača Unit, Flysch Belt of the Outer Western Carpathians. Detrital titanite and a Fe-Ti mineral (probably ilmenite) were almost completely altered to TiO₂ minerals, which also newly crystallized in intergranular spaces of sandstone. Brookite, anatase, and, exceptionally, rutile were identified by Raman spectroscopy. Authigenic TiO₂ phases show complex composition with occasionally elevated contents of Fe, Nb, Zr, V, Sc, Cr, Al, Y, and/or P, which were likely sourced from altered neighboring heavy minerals. In addition, rare authigenic LREE- and Y-enriched apatite rims were observed on detrital apatite. The remobilization of REE, Y, and HFSE was likely mediated by acidic early diagenetic fluids enriched in fluoride and sulfate anions. The superimposed formation of calcite cement was associated with the dissolution of detrital garnet, feldspars, and quartz. The compositions of detrital apatite and garnet (Alm_60-82Prp_4-30Sps_0-24Grs_0-19) are comparable with those from adjacent parts of the Flysch Belt. Detrital rutile is enriched in Nb, V, Cr, and Zr. Our study illustrates the intensity of diagenetic alteration of detrital minerals in flysch sandstones as well as the usefulness of in-situ electron-microprobe investigations for the recognition of processes influencing heavy minerals in diagenetically altered sediments. Full article

Composites made from carbon and nanominerals show great potential for thermal phase change materials, environmental water treatment, and biomass conversion. In 2019, a micro and nano-quartz-carbon ore was discovered in Feng-cheng City, Jiangxi Province. The study of the structural and physicochemical changes of quartz-carbon ore (QZC) during calcination is essential for the preparation of QZC-based composites and to broaden their application areas. Firstly, the SiO₂ crystal structure evolution of QZC during calcination was investigated using in-situ X-ray diffraction (XRD), ²⁹Si magic-angle sample spinning nuclear magnetic resonance (MAS NMR), and Fourier transform infrared FTIR spectroscopy. Then, the changes in carbon during calcination were investigated using Raman spectroscopy, ¹³C MAS NMR, and X-ray photoelectron spectroscopy (XPS). In addition, changes in the QZC morphology were observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. Finally, the evolution of the physicochemical properties of QZC during calcination was revealed using thermogravimetric (TG), Brunauer–Emmet–Teller (BET), resistivity, thermal conductivity, and zeta potential techniques. Full article

This paper reports the conversion of a waste to a conducting material, exploiting the ability to adsorb pollutant organic dyes. Leather waste was carbonized at 800 °C in an inert nitrogen atmosphere. The resulting biochar was used for in-situ deposition of polypyrrole nanotubes produced by the oxidative polymerization of pyrrole in the presence of methyl orange. The composites of carbonized leather with deposited polypyrrole nanotubes of various composition were compared with similar composites based on globular polypyrrole. Their molecular structure was characterized by infrared and Raman spectra. Both conducting components formed a bicontinuous structure. The resistivity was newly determined by a four-point van der Pauw method and monitored as a function of pressure applied up to 10 MPa. The typical conductivity of composites was of the order of 0.1 to 1 S cm⁻¹ and it was always higher for polypyrrole nanotubes than for globular polypyrrole. The method also allows for the assessment of mechanical features, such as powder fluffiness. The conductivity decreased by 1–2 orders of magnitude after treatment with ammonia but still maintained a level acceptable for applications operating under non-acidic conditions. The composites were tested for dye adsorption, specifically cationic methylene blue and anionic methyl orange, using UV-vis spectroscopy. The composites were designed for future use as functional adsorbents controlled by the electrical potential or organic electrode materials. Full article

Rechargeable magnesium batteries are an attractive alternative to lithium batteries because of their higher safety and lower cost, being spinel-type materials promising candidates for their positive electrode. Herein, MgMn₂O₄ with a tetragonal structure is synthesized via a simple, low-cost Pechini methodology and tested in aqueous media. Electrochemical measurements combined with in-situ Raman spectroscopy and other ex-situ physicochemical characterization techniques show that, in aqueous media, the charge/discharge process occurs through the co-intercalation of Mg²⁺ and water molecules. A progressive structure evolution from a well-defined spinel to a birnessite-type arrangement occurs during the first cycles, provoking capacity activation. The concomitant towering morphological change induces poor cycling performance, probably due to partial delamination and loss of electrical contact between the active film and the substrate. Interestingly, both MgMn₂O₄ capacity retention and cyclability can be increased by doping with nickel. This work provides insights into the positive electrode processes in aqueous media, which is vital for understanding the charge storage mechanism and the correlated performance of spinel-type host materials. Full article

To make supercapattery devices feasible, there is an urgent need to find electrode materials that exhibit a hybrid mechanism of energy storage. Herein, we provide a first report on the capability of lithium manganese sulfates to be used as supercapattery materials at elevated temperatures. Two compositions are studied: monoclinic Li₂Mn(SO₄)₂ and orthorhombic Li₂Mn₂(SO₄)₃, which are prepared by a freeze-drying method followed by heat treatment at 500 °C. The electrochemical performance of sulfate electrodes is evaluated in lithium-ion cells using two types of electrolytes: conventional carbonate-based electrolytes and ionic liquid IL ones. The electrochemical measurements are carried out in the temperature range of 20–60 °C. The stability of sulfate electrodes after cycling is monitored by in-situ Raman spectroscopy and ex-situ XRD and TEM analysis. It is found that sulfate salts store Li⁺ by a hybrid mechanism that depends on the kind of electrolyte used and the recording temperature. Li₂Mn(SO₄)₂ outperforms Li₂Mn₂(SO₄)₃ and displays excellent electrochemical properties at elevated temperatures: at 60 °C, the energy density reaches 280 Wh/kg at a power density of 11,000 W/kg. During cell cycling, there is a transformation of the Li-rich salt, Li₂Mn(SO₄)₂, into a defective Li-poor one, Li₂Mn₂(SO₄)₃, which appears to be responsible for the improved storage properties. The data reveals that Li₂Mn(SO₄)₂ is a prospective candidate for supercapacitor electrode materials at elevated temperatures. Full article

Biochar derived from waste biomass has proven to be an encouraging novel electrode material in supercapacitors. In this work, luffa sponge-derived activated carbon with a special structure is produced through carbonization and KOH activation. The reduced graphene oxide (rGO) and manganese dioxide (MnO₂) are in-situ synthesized on luffa-activated carbon (LAC) to improve the supercapacitive behavior. The structure and morphology of LAC, LAC-rGO and LAC-rGO-MnO₂ are characterized by the employment of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), BET analysis, Raman spectroscopy and scanning electron microscopy (SEM). The electrochemical performance of electrodes is performed in two and three-electrode systems. In the asymmetrical two-electrode system, the LAC-rGO-MnO₂//Co₃O₄-rGO device shows high specific capacitance (SC), high-rate capability and excellent cycle reversibly in a wide potential window of 0–1.8 V. The maximum specific capacitance (SC) of the asymmetric device is 586 F g⁻¹ at a scan rate of 2 mV s⁻¹. More importantly, the LAC-rGO-MnO₂//Co₃O₄-rGO device exhibits a specific energy of 31.4 W h kg⁻¹ at a specific power of 400 W kg⁻¹. Overall, the synergistic effect between the ternary structures of microporous LAC, rGO sheets and MnO₂ nanoparticles leads to the introduction of high-performance hierarchical supercapacitor electrodes. Full article

Photovoltaics are being transformed by perovskite solar cells. The power conversion efficiency of these solar cells has increased significantly, and even higher efficiencies are possible. The scientific community has gained much attention due to perovskites’ potential. Herein, the electron-only devices were prepared by spin-coating and introducing the organic molecule dibenzo-18-crown-6 (DC) to CsPbI₂Br perovskite precursor solution. The current-voltage (I-V) and J-V curves were measured. The morphologies and elemental composition information of the samples were obtained by SEM, XRD, XPS, Raman, and photoluminescence (PL) spectroscopies. The distinct impact of organic DC molecules on the phase, morphology, and optical properties of perovskite films are examined and interpreted with experimental results. The efficiency of the photovoltaic device in the control group is 9.76%, and the device efficiency gradually increases with the increase of DC concentration. When the concentration is 0.3%, the device efficiency is the best, reaching 11.57%, short-circuit current is 14.01 mA/cm², the open circuit voltage is 1.19 V, and the fill factor is 0.7. The presence of DC molecules effectively controlled the perovskite crystallization process by inhibiting the in-situ generations of impurity phases and minimizing the defect density of the film. Full article

This study explores the electrochemical reduction in CO₂ using room temperature ionic liquids as solvents or electrolytes, which can minimize the environmental impact of CO₂ emissions. To design effective CO₂ electrochemical systems, it is crucial to identify intermediate surface species and reaction products in situ. The study investigates the electrochemical reduction in CO₂ using a cobalt porphyrin molecular immobilized electrode in 1-n-butyl-3-methyl imidazolium tetrafluoroborate (BMI.BF4) room temperature ionic liquids, through in-situ surface-enhanced Raman spectroscopy (SERS) and electrochemical technique. The results show that the highest faradaic efficiency of CO produced from the electrochemical reduction in CO₂ can reach 98%. With the potential getting more negative, the faradaic efficiency of CO decreases while H₂ is produced as a competitive product. Besides, water protonates porphyrin macrocycle, producing pholorin as the key intermediate for the hydrogen evolution reaction, leading to the out-of-plane mode of the porphyrin molecule. Absorption of CO₂ by the ionic liquids leads to the formation of BMI·CO₂ adduct in BMI·BF₄ solution, causing vibration modes at 1100, 1457, and 1509 cm⁻¹. However, the key intermediate of ${\mathrm{CO}}_2^{-}·$ radical is not observed. The υ(CO) stretching mode of absorbed CO is affected by the electrochemical Stark effect, typical of CO chemisorbed on a top site. Full article

This work investigates the effects of oxygen and humidity on black phosphorous (BP) and black arsenic phosphorous (${\mathrm{As}}_{\mathrm{x}}{\mathrm{P}}_{1-\mathrm{x}}$ ) flakes using Raman spectroscopy and in situ electric transport measurements (four-probe resistance and thermoelectric power, TEP). The results show that the incorporation of arsenic into the lattice of BP renders it more stable, with the degradation times for BP, ${\mathrm{As}}_{0.2}{\mathrm{P}}_{0.8}$, and ${\mathrm{As}}_{0.4}{\mathrm{P}}_{0.6}$ being 4, 5, and 11 days, respectively. The P-P Raman peak intensities were determined to decrease with exposure to oxygen and moisture. The TEP measurements confirmed that both BP and ${\mathrm{As}}_{\mathrm{x}}{\mathrm{P}}_{1-\mathrm{x}}$are p-type semiconductors with the TEP of ${\mathrm{As}}_{0.4}{\mathrm{P}}_{0.6}$ stabilizing more slowly than that of BP. In addition, the four-probe resistance of BP and ${\mathrm{As}}_{\mathrm{x}}{\mathrm{P}}_{1-\mathrm{x}}$ stabilized significantly faster when exposed to air after being degassed in a vacuum. This was attributed to the charge transfer between the oxygen redox potential of air and the Fermi energy (E_F) of the semiconductors. Full article

The in-situ Raman spectroscopy oxidation of the accordion-like V₂CT_x MXene has been studied. It was found that a nanocomposite of V₂CT_x/V₃O₇ composition was formed as a result. The elemental and phase composition, the microstructure of the synthesized V₂CT_x powder and MXene film as well as the V₂CT_x/V₃O₇ nanocomposite obtained at a minimum oxidation temperature of 250 °C were studied using a variety of physical and chemical analysis methods. It was found that the obtained V₂CT_x and V₂CT_x/V₃O₇ films have an increased sensitivity to ammonia and nitrogen dioxide, respectively, at room temperature and zero humidity. It was shown that the V₂CT_x/V₃O₇ composite material is characterized by an increase in the response value for a number of analytes (including humidity) by more than one order of magnitude, as well as a change in their detection mechanisms compared to the individual V₂CT_x MXene. Full article

We report on the synthesis of activated carbon-semi-polycrystalline polyaniline (SPani-AC) composite material using in-situ oxidative polymerization of aniline on the carbon surface in an aqueous HCl medium at an elevated temperature of 60 °C. The electroactive polymeric composite material exhibits a uniformly distributed spindle-shaped morphology in scanning electron microscopy (SEM) and well-defined crystallographic lattices in the high-resolution transmission electron microscopy (TEM) images. The X-ray diffraction (XRD) spectrum reveals sharp peaks characteristic of crystalline polyaniline. The characteristic chemical properties of polyaniline are recorded using laser Raman spectroscopy. The cyclic voltammetry curves exhibit features of surface-redox pseudocapacitance. The specific capacitance calculated for the material is 507 F g⁻¹ at the scan rate of 10 mV s⁻¹. The symmetrical two-electrodes device exhibits a specific capacitance of 45 F g⁻¹ at a current density of 5 A g⁻¹. The capacitive retention calculated was found to be 96% up to 4500 continuous charge–discharge cycles and observed to be gradually declining at the end of 10,000 cycles. On the other hand, Coulombic efficiency was observed to be retained up to 85% until 4500 continuous charge–discharge cycles which declines up to 72% at the end of 10,000 cycles. The article also presents a detailed description of material synthesis, the formation of polyaniline (Pani) chains, and the role of material architecture in the performance as surface redox supercapacitor electrode. Full article

This study presents a non-invasive in situ methodology based on the use of portable elemental (energy dispersive X-ray fluorescence spectroscopy, EDXRF) and molecular (Raman spectroscopy) spectroscopic-based instrumentation as a tool to obtain preliminary information to assist subsequent provenance studies of archaeological cinnabar pigments in the laboratory. In this work, six cinnabar mineral ores, extracted from the Almadén mining district and an original raw pigment coming from the Archaeological Park of Pompeii have been analyzed. As the detection capacities and spectral resolution of the portable instruments are usually poorer than the equivalent benchtop equipment, a comparative study of the in-situ and laboratory results was conducted. Afterward, chemometric data treatment was performed considering both the molecular and elemental information. According to the elemental results, it was not possible to find a strong concordance between the cinnabar ores and the pigment from Pompeii, suggesting the need for additional methodologies in the laboratory (isotope ratio analysis) to complete a proper provenance study. However, this approach was useful to classify the ores according to their mineralogical differences. Therefore, this methodology could be proposed as a useful tool to conduct a representative sampling of the cinnabar mineral ores to be considered in a provenance study of archaeological cinnabar pigments. Full article