Raman Spectroscopy Research Articles

The isosbestic point in the Raman spectra of the hydration shell

Isosbestic point is often observed in a series of spectra, but their interpretation is still controversial, such as whether the continuum model can produce an isosbestic point. In order to answer this question, the Raman spectra of hydration shell with continuous distribution structure in different ionic aqueous solutions were separated by Raman ratio spectra, and an isosbestic point was successfully observed. Our experimental results show that the continuum model can indeed produce the isosbestic point. In order to deepen the understanding of the isosbestic point, we calculate the first moment of the Raman spectra and conduct molecular dynamics (MD) simulations. Both experimental and theoretical findings indicate that elevated temperatures lead to increased disorder among water molecules within the hydration shell.

Thermal decomposition of oxygen‐containing Ta3N5${\rm {Ta}}_3{\rm {N}}_5$

AbstractTransition metal nitrides, especially tantalum nitrides, are pivotal for applications in extreme environments demanding excellent mechanical properties and thermodynamic stability. Among them, ‐TaN, a high‐pressure polymorph of tantalum nitride with its exceptional bulk modulus (362 GPa) and hardness (31.7 GPa) promises to have many technological uses. Another nitride, , has gained importance as a photocatalyst for water splitting using visible light. The Ta–N phase diagram indicates that the thermal decomposition of pure leads to the formation of ‐TaN. However, usually has some amount of oxygen as an impurity mainly due to its synthesis route. We found that the ‐TaN phase, which is usually observed at high pressures, is formed during the thermal decomposition of oxygen containing . The presence of ‐TaN is verified using several experimental techniques such as X‐ray diffraction, Raman spectra, high‐angle annular dark field scanning transmission electron microscopy (STEM‐HAADF), and electron energy loss spectroscopy (EELS). Elemental distribution analyzed through energy dispersion X‐ray spectroscopy (XEDS) in STEM reveals about 7 at.% of oxygen in ‐TaN. First‐principle calculations are performed to examine the thermodynamic stability of oxygen substituted ‐TaN and pure ‐TaN via formation enthalpies, elastic constants, and phonon dispersion calculations. The computational studies confirm that oxygen in ‐TaN enhances its thermodynamic stability. The calculated electron localization functions establish the bonding characteristics between Ta, N, and O, confirming the same.

Phosphate geochronometer minerals: Crystal chemistry and radiation disorder, methodological issues of their microprobe non-isotope U–Th–Pb<sub>tot</sub> dating

Research subject. Phosphate mineral geochronometers – the international reference sample of Trebilcock monazite from pegmatites with the age of 272 ± 2 Ma, as well as samples of monazite from pegmatites of the Shartash massif and monazite, cheralite and xenotime from leucogranite of the Peshcherninsky stock and diorite of the Khomutinsky massif, Middle Urals. Methods. The composition of minerals was studied using CAMECA SX100 microprobe; Raman spectra were obtained using LabRAM HR800 Evolution confocal spectrometer. Research aim. Study of the internal texture of the grains of phosphate minerals on the basis of their elemental and spectroscopic mapping; analysis of the mineral crystal chemistry and estimation of auto-irradiation doses; microprobe non-isotopic U–Th–Pbtot dating of phosphate minerals; development of the appropriate algorithm for using analytical techniques. Results. It has been shown that the studied monazites belong to the cerium variety with ThO2 content from 1.1 to 17.2; UO2 – from 0 to 0.8; PbO – from 0.01 to 0.23 wt % (detection limits 160, 230, and 110 ppm). When analyzing the PbO content, the background line was interpolated into models of linear background (Trebilcock monazite, monazite and cheralite of the Peshcherninsky stock) and exponential background (monazite of the Shartash massif). It has been shown that for monazite, both huttonite and cheralite types of isomorphism are realized; the non-stoichiometric parameter of its composition β = (Si + Ca)/(Th + U + Pb + S) lies in the range of 0.95–1.05, which indicates the preservation of the U–Th–Pb-system. The analysis of BSE-images, intensity distribution maps of the Th Mα and Pb Mα RE lines, compositional point analyses and the results of spectroscopic mapping of the parameters of the ν1(PO4) vibrational mode testify to high homogeneity of Trebilcock monazite and pronounced zoning of the Ural monazites. It has been shown that the parameters of the ν1(PO4) vibrational mode in monazites are determined by the superposition of two factors, i.e. chemical and radiation disorder. The data on U, Th, and Pb content for different zones of monazite grains were used to perform non-isotopic U–Th–Pbtot dating: weighted average age values for the zones were obtained, and isochron plotting was made on the ThO2* vs. PbO diagram. The datings obtained based on the Trebilcock sample are in satisfactory agreement with the literature. Conclusions. The dating of monazite from leucogranite of the Peshcherninsky stock and the Shartash massif are in agreement with the U-Pb isotopic dating of zircon. The physical and chemical characteristics of cheralite, xenotime, and zircon in samples from the Peshcherninsky stock were analyzed. The U–Th–Pbtot dating of cheralite, xenotime, and zircon was attempted. The described algorithm and analytical methods were used at the Geoanalitik Common Use Center for microprobe non-isotopic dating of phosphate minerals.

Post-synthetic Metalation on the Ionic TiO2 Surface to Enhance Metal-CO2 Interaction During Photochemical CO2 Reduction.

During the photochemical CO2 reduction reaction, CO2 adsorption on the catalyst's surface is a crucial step where the binding mode of the [metal-CO2] adduct directs the product selectivity and efficiency. Herein, an ionic TiO2 nanostructure stabilized by polyoxometalates (POM), ([POM]x@TiO2), is prepared and the sodium counter ions present on the surface to balance the POMs' charge are replaced with copper(II) ions, (Cux[POM]@TiO2). The microscopic and spectroscopic studies affirm the copper exchange without altering the TiO2 core and weak coordination of copper (II) ions to the POMs' surface. Band structure analysis suggests the photo-harvesting efficiency of the TiO2 core with the conduction band edge higher than the reduction potential of CuII/I and multi-electron CO2 reduction potentials. Photochemical CO2 reduction with Cux[POM]@TiO2 results in 30 µmol gcat.-1 CO (79%) and 8 µmol gcat-1 of CH4 (21%). Quasi-in-situ Raman study provides evidence in support of CO2 adsorption on the Cux[POM]@TiO2 surface. 13C and D2O labeling studies validates the {Cu-[CO2]-} adduct formation. Despite the photo-harvesting ability of Nax[POM]@TiO2 itself, the poor CO2 adsorption ability of sodium ions highlights the crucial role of copper ion CO2 photo-reduction. Characterization of the {M-[η2-CO2]-} species via surface tuning validates the CO2 activation and photochemical reduction pathway proposed earlier.

Operando insights into ammonium-mediated lithium metal stabilization: surface morphology modulation and enhanced SEI development

Lithium-ion batteries (LiBs) with graphite as an anode and lithiated transition metal oxide as a cathode are approaching their specific energy and power theoretical values. To overcome the limitations of LiBs, lithium metal anode with high specific capacity and low negative redox potential is necessary. However, practical application in rechargeable cells is hindered by uncontrolled lithium deposition manifesting, for instance, as Li dendrite growth which can cause formation of dead Li, short circuits and cell failure.The electrochemical behaviour of a protic additive (NH4PF6) in a carbonate-based electrolyte has been investigated by operando confocal Raman spectroscopy, in situ optical microscopy, and X-ray photoelectron spectroscopy, elucidating its functional mechanism. The ammonium cation promotes a chemical modification of the lithium metal anode-electrolyte interphase by producing an N-rich solid electrolyte interphase and chemically modifying the lithium surface morphology by electrochemical pitting. This novel method results in stable lithium deposition and stripping by a decreasing the local current density on the electrode, thus limiting dendritic deposition.

An Exploration of Cysteamine as a Subphase Additive for the Fabrication of Uniform Gold Nanorod Arrays using Langmuir-Blodgett Deposition.

Gold nanorods (AuNRs) have attracted significant attention over the past several decades for a variety of applications and there has been steady progress with regards to their synthesis and modification. Despite these advances, the assembly of AuNRs into well-organized hierarchical assemblies remains a formidable challenge. Specifically, there is a need for tools that can fabricate assemblies of nanorods over large length scales at low cost with the potential for high-throughput manufacturing. Langmuir-Blodgettry is a monolayer deposition technique which has been primarily applied to amphiphilic molecules, but which has recently shown promise for the ordering of functionalized nanoparticles residing at the air-water interface. In this work, Langmuir-Blodgett deposition is explored for the formation of AuNR arrays for enhanced surface-enhanced Raman spectroscopy (SERS) sensing.In particular, both surface modification of the AuNRs as well as subphase modification with cysteamine were evaluated for AuNR array fabrication.

An investigation of slurry erosion behaviour in plasma-sprayed carbon nanotube-reinforced fly ash/alumina coatings using experimental analysis and artificial neural computing for marine and offshore applications

This study investigates carbon nanotube (CNT)-reinforced alumina fly ash (FA) coatings, namely AF (unreinforced), 1CAF (with 1 wt% CNT), and 2CAF (with 2 wt% CNT), on marine-grade steel. Microstructural analysis shows 1CAF coatings denser by ∼15.32% due to CNT reinforcement, while 2CAF coatings display ∼9.68% increased porosity from CNT agglomeration. Raman spectroscopy confirms CNT retention. 1CAF coatings exhibit ∼14.66% higher microhardness, ∼15.96% higher adhesion strength, and ∼15.66% improved fracture toughness compared to AF coatings, attributed to pore sealing through CNT reinforcement. Enhanced erosion resistance (∼14.59%) in 1CAF coatings was observed due to improved mechanical properties and CNTs mitigating crack propagation. Validation through an artificial neural network (ANN) modeling and regression analysis supports 1CAF coatings’ promise for harsh marine environments, offering enhanced durability.

Biochemical and immunomodulatory insights of extracellular matrix from decellularized human whole cervix: recellularization and in vivo ECM remodeling interplay

Extracellular matrix (ECM) rich whole organ bio-scaffolds, preserving structural integrity and essential growth factors, has potential towards regeneration and reconstruction. Women with cervical anomalies or trauma can benefit from clinical cervicovaginal repair using constructs rich in site specific ECM. In this study, complete human cervix decellularization was achieved using a modified perfusion-based stir bench top decellularization method. This was followed by physico-chemical processes including perfusion of ionic agents, enzymatic treatment and washing using detergent solutions for a duration of 10–12 d. Histopathological analysis, as well as DNA quantification confirmed the efficacy of the decellularization process. Tissue ultrastructure integrity was preserved and the same was validated via scanning electron microscopy and transmission electron microscopy studies. Biochemical analysis and structural characterizations like Fourier transform infrared, Raman spectroscopy of decellularized tissues demonstrated preservation of important proteins, crucial growth factors, collagen, and glycosaminoglycans. In vitro studies, using THP-1 and human umbilical vein endothelial cell (HUVEC) cells, demonstrated macrophage polarization from M1 to M2 and vascular functional genes enhancement, respectively, when treated with decellularized human cervical matrix (DHCp). Crosslinked DHC scaffolds were recellularized with site specific human cervical epithelial cells and HUVEC, showing non-cytotoxic cell viability and enhanced proliferation. Furthermore, DHC scaffolds showed immunomodulatory effects in vivo on small rodent model via upregulation of M2 macrophage genes as compared to decellularized rat cervix matrix scaffolds (DRC). DHC scaffolds underwent neo-vascularization followed by ECM remodeling with enhanced tissue integration.

Coupling Multidimensional Chromatography with Plasmonic Sensing: An Exploration of Electrochemical SERS as a Detection Modality for 2D-LC

Complex mixtures which may contain hundreds, if not thousands, of unique compounds pose an analytical challenge for complete and detailed analyses. For example, green tea is a well-known complex substance requiring advanced separation techniques and ultrasensitive detection methods for full characterization. Separation and identification of components in green tea help gauge tea quality, as green tea is one of the most consumed beverages in the world. In this work, the coupling of two-dimensional liquid chromatography (2D-LC) and electrochemical surface-enhanced Raman spectroscopy (EC-SERS) was explored for the first time to analyze compounds in green tea. 2D-LC offers enhanced separation compared to conventional HPLC systems due to the second dimension of separation. EC-SERS was used as an offline detection modality and qualitative tool to help identify the compounds in green tea fractions collected from the second dimension separation. 2D-LC and EC-SERS are coupled in this work for the first time and offer a pathway forward for sensitive and selective separation and identification of components in complex mixtures.

Durolon® polymer as a nuclear track detector: Characterization by chemical etching

This paper presents the properties of alpha particle tracks in a polymer, known as Durolon®. The study involves measurements of the time-dependent evolution of etch pit diameters and areal densities for low-energy alpha particles under various etching conditions, including different temperatures and solutions. A time-dependent model was successfully employed to describe the etch pit growth rates. Additionally, optical absorption and Raman spectroscopy techniques were applied to the samples under investigation, complementing the traditional results obtained through optical microscopy. The suitability of Durolon® polymer as a nuclear track detector is discussed based on the results obtained from the aforementioned complementary techniques. In summary, this research represents a critical step toward establishing Durolon® polymer as a viable nuclear track detector.

Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites

AbstractMetal‐based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X‐ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure–activity relationships of low‐crystalline cobalt sulfide (L−CoS) catalysts toward overall water splitting. The operando results for L−CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S−Co−Co−S moieties as the true catalytically active species. In comparison, during the acidic HER, L−CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co−S−Co configurations. Further operando characterizations highlight the crucial formation of high‐valent Co4+ species in L−CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co‐LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.

Operando Spectroscopic Monitoring of Metal Chalcogenides for Overall Water Splitting: New Views of Active Species and Sites.

Metal-based chalcogenides exhibit great promise for overall water splitting, yet their intrinsic catalytic reaction mechanisms remain to be fully understood. In this work, we employed operando X-ray absorption (XAS) and in situ Raman spectroscopy to elucidate the structure-activity relationships of low-crystalline cobalt sulfide (L-CoS) catalysts toward overall water splitting. The operando results for L-CoS catalyzing the alkaline hydrogen evolution reaction (HER) demonstrate that the cobalt centers in the bulk are predominantly coordinated by sulfur atoms, which undergo a kinetic structural rearrangement to generate metallic cobalt in S-Co-Co-S moieties as the true catalytically active species. In comparison, during the acidic HER, L-CoS undergoes local structural optimization of Co centers, and H2 production proceeds with adsorption/desorption of key intermediates atop the Co-S-Co configurations. Further operando characterizations highlight the crucial formation of high-valent Co4+ species in L-CoS for the alkaline oxygen evolution reaction (OER), and the formation of such active species was found to be far more facile than in crystalline Co3O4 and Co-LDH references. These insights offer a clear picture of the complexity of active species and site formation in different media, and demonstrate how their restructuring influences the catalytic activity.

Diagnostic Accuracy of Raman Spectroscopy Integrated With Polarized Light Microscopy for Calcium Pyrophosphate-Associated Arthritis.

We studied the performance of integrated Raman polarized light microscopy (iRPolM) for the identification of calcium pyrophosphate (CPP)-associated arthritis (CPPD). This is a diagnostic accuracy study including 400 consecutive synovial fluid samples from a single hospital in the Netherlands. Accuracy measures were calculated against polarized light microscopy (PLM) and the 2023 American College of Rheumatology (ACR)/EULAR criteria set for CPPD. The interrater reliability between iRPolM and the 2023 ACR/EULAR criteria set for CPPD was strong (κ = 0.88). The diagnostic performance of iRPolM compared to the 2023 ACR/EULAR criteria set was sensitivity 86.0% (95% confidence interval [CI] 73.3-94.2), specificity 99.1% (95% CI 97.5-99.8), positive likelihood ratio 100.33 (95% CI 32.3-311.3), negative likelihood ratio 0.14 (95% CI 0.07-0.28), positive predictive value 93.5% (95% CI 82.2-97.8), negative predictive value 98.0% (95% CI 82.2-97.8), and accuracy 97.5% (95% CI 95.5-98.8). We allowed rheumatologists to rate the certainty of their microscopic identification of CPP and found a large correspondence between iRPolM and a certain identification (κ = 0.87), whereas only 10% of the uncertain CPP identifications could be confirmed with iRPolM. We identified several novel particle types in synovial fluid analysis, including calcium carbonate crystals, deposited carotenoids, microplastics, and three types of Maltese cross birefringent objects. iRPolM can easily identify CPP crystals with a strong diagnostic performance. PLM alone is not specific enough to reliably resolve complicated cases, and the implementation of Raman spectroscopy in rheumatology practice can be of benefit to patients with suspected CPPD.

Ultrafast planarization of photoexcited ligands in metal–organic frameworks gates charge transfer to promote photocatalysis

Metal–organic frameworks (MOFs) have emerged as a highly tunable class of porous materials with wide-ranging applications from gas capture to photocatalysis. Developing these exciting properties to their fullest extent requires a thorough mechanistic understanding of the structure–function relationships. We implement an ultrafast spectroscopic toolset, femtosecond transient absorption and femtosecond stimulated Raman spectroscopy (FSRS), to elucidate the correlated electronic and vibrational dynamics of two isostructural 1,3,6,8-tetrakis(p-benzoic acid)pyrene (TBAPy)-based MOFs, which manifest drastically different photocatalytic behaviors. Systematic comparisons between the M3+-TBAPy MOFs and bare ligands in various environments reveal the unproductive dimer formation in Al-TBAPy, whereas Sc-TBAPy is dominated by a catalytically active charge-transfer (CT) process. Two ground-state FSRS marker bands of the TBAPy ligand at ∼1267 and 1617 cm−1 probe the chromophore environment at thermal equilibrium. For comparison, the excited-state FSRS of Sc-TBAPy suspended in neutral water unveils a key ∼300 fs twisting motion of the TBAPy peripheral phenyl groups toward planarity, promoting an efficient generation of CT species. This motion also exhibits high sensitivity to solvent environment, which can be a useful probe; we also showed the CT variation for ultrafast dynamics of Sc-TBAPy in the glyphosate aqueous solution. These new insights showcase the power of table-top tunable FSRS methodology to delineate structural dynamics of functional molecular systems in action, including MOFs and other photosensitive “nanomachines.” We expect the uncovered ligand motions (ultrafast planarization) to enable the targeted design of new MOFs with improved CT state characteristics (formation and lifetime) to power applications, including photocatalysis and herbicide removal from waterways.

Determination of the internal structural heterogeneity of natural diamond: Methodological aspects of using confocal Raman spectroscopy with polarization analysis

Aim. To describe a technique for studying the internal structural heterogeneity of natural diamond crystals, based on confocal Raman spectroscopy with polarization analysis, including angular resolution, at high spectral (0.5–0.6 cm–1) and spatial (1 μm) resolution. Results. The parameters of the F2g vibrational mode in diamond (position, width, intensity, shape, including the Gaussian and Lorentzian contributions to the broadening) are determined by the superposition influence of a number of factors, including the type and content of structural stresses, deformations, various types of defects, as well as orientation of crystallographic axes of the crystal relative to the directions of incident and scattered rays and the directions of their electric polarization vectors. The proposed analytical technique includes: (1) analysis of the crystallographic orientation of the sample in the spectrometer coordinate system and possible misorientations of its fragments with an error of ≈8–15°; (2) visualization of the distribution of structural stresses, deformations, twins, impurity defects and their associates based on sample surface mapping by spectral parameters of the F2g vibration mode; (3) obtaining statistical characteristics of the internal structural heterogeneity of the samples based on diagrams of spectral parameter frequency with a statistically significant number (≈103): unimodality (uni-, bimodal distributions) and distribution dispersion (from ≈0.1 to ≈0.6 cm–1 for width and from ≈0.04 to ≈0.6 cm–1 for line position). The procedure was tested using two synthetic CVD diamond single crystals doped with nitrogen and boron. The possibility of typification of natural samples by statistical characteristics of internal heterogeneity is considered using the example of samples from kimberlite pipes of Yakutia and placers of the Western Cis-Urals. Conclusions. A method for determining the internal structural heterogeneity of natural diamond crystals based on confocal Raman spectroscopy with polarization analysis is proposed. The possibility of using statistical characteristics of heterogeneity as a typomorphic feature of the original diamond source is demonstrated. The proposed diagrams are promising for sample comparison and typification.

Opportunities and Challenges: Process Raman for the Real-Time Release Testing (RTRT) of Extended-Release Formulations

The use of a process analytical technology has been demonstrated using near-infrared spectroscopy for continuous manufacturing of pharmaceutical formulations and is within the scope of the U.S. Food and Drug Administration's real-time release testing initiative. While effective for simple formulations, this preliminary study investigates whether such a spectroscopic surrogate application can replace pharmaceutical dissolution testing for extended-release formulations. In this study, we will assess the use of process Raman spectroscopy for real-time dissolution testing. Extended-release tablet formulations often accomplish the release rate delay through the addition of gelling agents. In this work, hydroxypropyl methylcellulose (HPMC) polymers were used to formulate extended-release niacin tablets. Process Raman spectroscopy was evaluated as a tool to effectively model dissolution profiles to determine if the optical technique has the ability to differentiate HPMC polymers from the background and be selective for the polymer type employed. Our preliminary work indicates that while Raman can effectively detect and monitor the niacin response of the tablet formulations, there are not enough unique spectral features between the different HPMC polymers to selectively resolve their responses. Additional measurements and chemometric analysis might suggest otherwise. Thus, for extended-release tablet applications with continuous manufacturing, further dissolution surrogate development is needed.

Staggered band alignment – direct Z-scheme for photocatalytic activity in Stibnite/rGO layered nanohybrids

Type-II staggered band aligned layered nanohybrids (LNHs) satisfy the unique characteristics required for photocatalysts. Here, the spin-assisted layer-by-layer deposition (SA-LBL) of stibnite/reduced graphene oxide (Sb2S3/rGO) LNHs are fabricated and their structural, morphological, electrical, and optical properties are reported. From the FESEM analysis, it was found that with increasing rGO content, the morphology of Sb2S3 nanoparticles changed from the granular to nanorods which might be due to Ostwald ripening or microstructural coarsening effect. Further, Raman spectroscopy proves that the B1 g and Ag of Sb2S3 decrease by the addition of rGO mainly due to the electron-phonon interaction. Based on the estimation of valence band edge and conduction band edge of Sb2S3/rGO LNHs using X-ray photoelectron spectroscopy and optical studies, we propose that the interface in Sb2S3/rGO LNHs is a type-II staggered band alignment Direct Z-scheme. The increased spatial charge separation and carrier lifetime of Sb2S3/rGO LNHs materials results in opening a new pathway to explore and extend their applications as photocatalysts.

Structural, Dielectric, Electrical, and Magnetic Characteristics of Bi0.8Ba0.1Er0.1Fe0.96Cr0.02Mn0.02O3 Nanoparticles

Bi0.8Ba0.1Er0.1Fe0.96Cr0.02Mn0.02O3 (BBEFCMO) multiferroic ceramic was synthesized through the sol-gel route. The impact of incorporating various dopants into both A and B sites of the BiFeO3 was investigated, and structural, Raman, dielectric, electric, and magnetic properties were studied. X-ray diffraction analysis and Raman spectroscopy revealed a rhombohedral structure with the R3c space group for the doped material (BBEFCMO). Dielectric properties were examined across a frequency range of 102–106 Hz. The present multiferroic material exhibits a colossal dielectric constant and minimal dielectric loss tangent, making it suitable for applications in energy storage. Furthermore, the Cole-Cole type of relaxation was deduced from the imaginary part of the modulus for both grain and boundary-grain contributions. Overall, this study indicates that substituting ions in both A and B sites of BiFeO3 significantly enhances its multiferroic properties, as evidenced by dielectric and magnetic measurements.

Unleashing Ultrahigh Capacity and Lasting Stability: Aqueous Zinc‐Sulfur Batteries

AbstractDespite of multifarious dominance of sulfur‐based batteries, polysulfide‐shuttling and use of high‐cost organic electrolytes with flammability risks hinder their applicability as commercial devices. Herein a polysulfide‐free aqueous zinc‐sulfur (Zn─S) rechargeable battery is explored, which offers a low‐cost and environmentally friendly energy storage system being Zn and Sulfur (S) highly abundant with high theoretical capacity. However, the stability of Zn anode is quite challenging due to dendritic growth and corrosion leading to the capacity decay. This work showcases the utilization of ethylene glycol (EG) and iodine (I2) as an electrolyte additive in aqueous zinc acetate [Zn(OAc)2] electrolyte for stabilizing the Zn─S battery performance. EG as an additive is able to mitigate the corrosion rate of the Zn electrode by 15 times which is supported by molecular dynamics simulation. The assembled Zn─S battery delivered an outstanding capacity of 1210 mA h g−1 at 0.1 C with a 91% capacity retention even after 250 cycles, along with remarkable reversible prolonged cycling stability of 3000 cycles at 1 C, with 64.5% capacity retention. More importantly, in situ electrochemical Raman spectroscopy is utilized to monitor the real‐time formation of zinc sulfide (ZnS) as a single discharge product and simultaneously debunking the polysulfide shuttling in the system which is further supported by XPS, UV‐Vis and IR spectroscopy.

Asian clam Corbicula fluminea as potential biomonitor of microplastics and metal(oid)s in a Patagonian River

This study summarizes the concentration in dry weight (dw) of several metal(oid)s (As, Cd, Cr, Cu, Mn, Ni, Pb, and Zn), as well as the abundance and characteristics of microplastics (MP) in wet weight (ww) of the soft tissues of clam Corbicula fluminea from Chubut River (Patagonia, Argentina). The contents of essential elements were in the following decreasing order: Zn > Mn > Cu > Ni; meanwhile, non-essential elements Cd, Cr and Pb were below the detection limit (<0.5 μg/g dw). A high mean concentration of As (6.1 ± 0.3 μg/g dw) was found, surpassing the maximum allowable limit established by the Argentine Food Code for bivalve molluscs. The number of MP ranged from 0.07 to 1.27 items/ind. and from 0.2 to 2.9 items/g ww. Fibers were the most common shape, mainly transparent. The size of MP ranged from 42 to 1917 μm, accounting for 62 % of MP between 50 and 450 μm. The dominant polymer was PET based on the results of Raman spectroscopy. Based on the widespread distribution of MP in the environment and the wide range of effects on organisms, it is necessary to develop long-term monitoring programs for MP contamination in different environmental matrices. Understanding the bioaccumulation of MP in bivalves is crucial to assess the potential risk to human health through consumption and to the ecosystem. We propose that the widespread Asian clam could serve as a useful biomonitor for MP and As pollution in freshwater and estuarine environments such as the Chubut River.