Intermediate Sulfur Research Articles

Thermithiobacillus plumbiphilus AAFK—Arsenic-Resistant Bacteria Isolated from Arsenopyrite Material

Autotrophic sulfur-oxidizing bacteria can play a key role in the metal bioleaching from low-grade sulfide-containing ores. The most commonly used bioleaching group is presented with acidophilic bacteria of the order Acidithiobacillales. We studied the diversity of bacteria in the arsenopyrite gold-bearing ore and also discovered a wide distribution of neutrophilic non-thermophilic bacteria Thermithiobacillus plumbiphilus in this ore, as well as its drainage and flotation concentrate. For the first time, T. plumbiphilus was isolated from the natural arsenic-containing mineral material. The first description of complete genome for the species T. plumbiphilus was also carried out and discovered genes providing the As resistance. Culturing the isolated strain T. plumbiphilus AAFK confirmed the found bacterial resistance to arsenite and cocadylate during the effective thiosulfate oxidation. Experiments on the arsenopyrite bioleaching showed that T. plumbiphilus AAFK can be used as an auxiliary bacterial culture capable of oxidizing reduced / intermediate sulfur compounds. The genetic basis of the T. plumbiphilus AAFK resistance to the arsenic compounds is discussed; the mechanisms are similar with the ones known for acidophilic thiobacilli. The biofilm formation is shown for the first time for T. plumbiphilus; presumably, it could provide some protection and immobilization of the cells. Structures of the T. plumbiphilus AAFK cells and their production of outer membrane vesicles are described and discussed.

Asymmetric Polarization Modulation of d-p Hybridization-Enhanced Bidirectional Sulfur Redox Kinetics with Heteronuclear Dual-Atom Catalysts.

Lithium sulfur batteries (LiSBs) represent a highly promising avenue for future energy storage systems, offering high energy density and eco-friendliness. However, the sluggish kinetics of the sulfur redox reaction (SRR) poses a significant challenge to their widespread applications. To tackle this challenge, we have developed an efficient heteronuclear dual-atom catalyst (hetero-DAC) that leverages surface charge polarization to enhance the asymmetric adsorption of sulfur intermediates. This study investigates how asymmetric electronic redistribution of CoFe DACs modulates the d-p orbital hybridization with sulfur intermediates, revealing the mechanisms of moderate adsorption dynamics with enhanced catalytic performance. The dynamic switching between mono and dual adsorption sites, enabled by the heteronuclear polarized configuration, fine-tunes the orbital hybridization, boosting the bidirectional rate-determining steps, that is, the solid-solid conversion of Li2S2 to Li2S and the reverse dissociation of Li2S. Consequently, the thus-designed CoFe DACs cathode delivers impressive rate performance, achieving a high initial specific capacity of 703.9 mA h g-1 at 3 C, with a negligible decay rate of only 0.031% over 1000 cycles, demonstrating sustained long-term cycling stability. This work bridges geometric configurations and electronic structures, elucidating the mechanisms of asymmetric trapping and conversion enabled by hetero-DACs and offering fresh perspectives for catalyst design in LiSBs and beyond.

Enhancing Performance of Lithium Sulfur Batteries with Electrode-Electrolyte Interphase Engineering

Batteries with high energy density are critical for the clean energy transition of human society. Lithium sulfur (Li-S) batteries with a high theoretical energy capacity is promising for applications such as electric vehicles. However, the commercialization obstacle of Li-S batteries lies on the shuttle effects of dissolved sulfur intermediates and formation of Li dendrite. In this work, we focus on engineering the electrode-electrolyte interphase with functionalized interlayers for enhanced performance of Li-S batteries. In particular, an amide-functionalized protection layer and a cellulose-based separator are employed, respectively. We discovered multifunctionality of these interlayers, including dendrite inhibition and shuttle effect suppression. A more conductive solid-electrolyte interphase (SEI) with high stability is demonstrated to form when these interlayers are used, via in-situ X-ray diffraction and impedance spectroscopy investigation. Our work paved a way to engineer electrode-electrolyte interphases in Li metal batteries without electrolyte additives.

Structure-activity relationship between crystal plane and pyrite-driven autotrophic denitrification efficacy: Electron transfer and metagenome-based microbial mechanism

Pyrite-driven autotrophic denitrification (PAD) has been recognized as a promising treatment technology for nitrate removal. Although the occurrence of PAD has been found in recent years, there is a knowledge gap about effects of crystal plane of pyrite on the performance and mechanism of PAD system. Here, this study investigated the effects of crystal planes ({100}, {111} and {210}) of single-crystal pyrite on denitrification performance, electron transfer, and microbial mechanism in PAD system. The removal efficiency of nitrate in B-{210} reached 100%, which was 1.67-fold and 2.86-fold higher than that of B-{100} and B-{111}, respectively. X-ray photoelectron spectroscopy and electrochemical results indicated that Fe-S bonds of pyrite with {210} crystal plane were more susceptible to breakage by Fe3+ oxidation assault, and leaching microbially available Fe2+ and sulfur intermediates to drive autotrophic denitrification. Metagenomic results suggested that community of functional pyrite-driven denitrifiers varied in response to crystal plane, and abundances of N-S transformation and EET-related microbes and genes in B-{210} notably up-regulated compared to B-{100} and B-{111}. In addition, this work proposed a dual-mode for electron transfer pathway during pyrite oxidation and nitrogen transformation in PAD system. In B-{210}, Fe(II)- and sulfur-driven denitrifiers obtained electron after pyrite oxidation-dissolution, and the enrichment of pyrite-oxidizing bacteria in B-{210} could enhance the electron transfer from pyrite through electron shuttles. This work highlighted that stronger surface reactivity and electron shuttle effect in B-{210} enhanced electron transfer, leading to favorable PAD performance in B-{210}. Overall, this study provides novel insights into the structure-activity relationship between the crystal plane structure of pyrite and denitrification activity in PAD system.

MOF-Derived Nitrogen-Rich Hollow Nanocages as a Sulfur Carrier for High-Voltage Aluminum Sulfur Batteries.

Aluminum-sulfur batteries (ASBs) are emerging as promising energy storage systems due to their safety, low cost, and high theoretical capacity. However, it remains a challenge to overcome voltage hysteresis and short cycle life in the sulfur/Al2S3 conversion reaction, which hinders the development of ASBs. Here, we studied a high-voltage ASB system based on sulfur oxidation in an AlCl3/urea electrolyte. Nitrogen-doped hollow nanocages (HNCs) synthesized from MOF precursors were rationally designed as sulfur/carbon composite electrodes (S@HNC), and the impact of the nitrogen species on the electrochemical performance of sulfur electrodes was systematically investigated. The S@HNC-900 achieved efficient conversion at 1.9 V, delivering a stable capacity of 197.3 mA h g-1 and a Coulombic efficiency of 93.28% after 100 cycles. Furthermore, the S@HNC-900 electrode exhibited exceptional rate capacity and 800th long-term cycling stability, retaining a capacity of 87.1 mA h g-1 at 500 mA g-1. Ex situ XPS and XRD characterizations elucidated the redox mechanism, revealing a four-electron transfer process (S/AlSCl7) at the S@HNC-900 electrode. Density functional theory calculations demonstrated that pyridinic nitrogen-enriched HNC-900 significantly enhanced the sulfur conversion reaction and facilitated the adsorption of sulfur intermediates (SCl3+) on the carbon interface. This work provides critical insights into the high-voltage sulfur redox mechanism and establishes a foundation for the rational design of carbon-based electrocatalysts for the enhancement of ASB performance.

Assembly of low-voltage driven co-production of hydrogen and sulfur via Ru nanoclusters on metal-sulfur coordination: Insights from DFT calculations

Herein, we propose a simple and rapid approach for synthesizing a CuS/Ru composite that serves as a bifunctional electrocatalyst to promote hydrogen production and concurrently convert sulfion into a value-added sulfur product. This composite comprises Ru nanoclusters supported on the CuS nanostructure, achieved through simple pulsed laser irradiation in liquid approach. The optimized CuS/Ru-30 electrocatalyst demonstrates remarkable bifunctional electrocatalytic activity, exhibiting a negligible working potential of 0.28 V (vs. RHE) for the anodic sulfion oxidation reaction (SOR) and a minimal overpotential of 182 mV for cathodic hydrogen evolution reaction (HER) to achieve 10 mA cm−2 of current density. Moreover, the CuS/Ru-30 electrocatalyst shows exceptional selectivity for converting sulfion into valuable sulfur during anodic oxidation reactions. Remarkably, in a two-electrode electrolyzer system utilizing CuS/Ru-30 as both the anode and cathode, the SOR + HER coupled water electrolysis system demands only 0.52 V to reach 10 mA cm−2, which is considerably lesser compared to the OER + HER coupled water electrolysis (1.85 V). The experimental results and density function theory (DFT) calculations reveal that the strong electron interaction between CuS and Ru nanoclusters generates a built-in electric field, greatly enhancing electron transfer efficiency. This significantly boosts the HER performance and facilitates the adsorption and production of sulfur intermediates. This study presents a rapid and simple strategy for synthesizing a dual-functional catalyst suitable for low-voltage hydrogen generation while facilitating the recovery of valuable sulfur sources.

Solvation-Property Relationship of Lithium-Sulfur Battery Electrolytes Probed via Potentiometric Measurements

The Li-S battery is a promising next-generation battery chemistry that offers high energy density and low cost. Li-S battery has a unique chemistry with intermediate sulfur species readily solvated in electrolytes, and understanding their implications is important from both practical and fundamental perspectives. However, the nature of the solvated sulfur species, their interactions and their impact on the battery remains elusive, in part due to the paucity of techniques. Recently, our group developed a potentiometric technique to probe the solvation free energy of electrolytes. In this study, we utilize the technique to formulate solvation-property relationships in various electrolytes and investigate its impact on the solvated lithium polysulides (LiPS). We find that solvation free energy impacts Li-S battery voltage profile, LiPS solubility, Li-S battery cyclability and the Li metal anode, which are all critical to the battery's performance. Weaker solvation leads to a lower 1st plateau voltage, higher 2nd plateau voltage, lower LiPS solubility, and superior cyclability of Li-S full cell and Li metal anode. We explore the mechanisms behind these observed phenomena and discuss the implications for the design of high-performance electrolytes for Li-S batteries.

(Invited) Lyten’s High Energy Li-S Batteries for a Sustainable and Circular EV Economy

Li-ion batteries (LIB), though widely used in EV batteries will be unable to meet the demands of the rapidly expanding vehicular market, mainly due to the challenges of cost and availability of key materials globally with limited resources, complicated by geopolitical factors. Li-S batteries promise significant advantages over Li-ion batteries with potentially higher specific energy, lower cost, and enhanced safety. However, their implementation has been hampered by poor cycle life due mainly to polysulfide shuttle caused by the soluble polysulfide intermediates. Lyten, an advanced materials company, has developed a family of new 3D Graphene™ materials for various applications including lithium-sulfur batteries. The mechanically flexible and electrically conductive framework of 3D graphene and its hierarchical porous structure make it an ideal host for potentially confining sulfur intermediates and mitigate the polysulfide shuttle. Lyten 3D Graphene™ materials have already shown enhanced sulfur utilization in Li-S cells far superior to the commercial nanocarbons (Fig. 1), even while their further fine-tuning is on-going. Lyten has established environmentally friendly 3D graphene-sulfur cathode fabrication methodology with high sulfur loadings using an aqueous binder.In parallel, Lyten has been developing new protected Li anodes, advanced stable electrolytes that can function at low quantities (electrolyte/sulfur ratio), and multi-functional separators with an ability to block polysulfide crossover. Integration of these cell components resulted in Li-S cells with specific energy comparable to current Li-ion cells (250-275 Wh/kg). The cycle life is, however, relatively modest with 300 cycles @ 100% DOD, C/3 in coin cells, and ~150 cycles@100% DOD and over one thousand cycles @ 50% DOD in multi-layer pouch cells and 18650 cylindrical cells. There is a steady growth in both these categories enabled by further tuning of 3D graphene and advances in other materials.Recently, Lyten has set up semi-automatic assembly lines for both multi-layer pouch and 18650 cylindrical cells, targeting an annual capacity of 2.4 MWh. These cells have started showing excellent consistency in specific energy in both cell formats. Fig.2 shows the narrow variability in the performance of 35 pouch and 18650 cells made recently for a customer.Finally, preliminary safety tests performed on the recent prototype cells have yielded surprisingly good results for the Li-S cells containing Li metal anode. Tolerance to usual abuse conditions, e.g., internal and external shorts, overcharge and overdischarge, as demonstrated in our ARC tests will be an additive advantage of Lyten Li-S cells. Figure 1

Reaction pathway, mechanism and kinetics of thermochemical sulfate reduction: insights from in situ Raman spectroscopic observations at elevated temperatures and pressures

In Earth’s crust, thermochemical sulfate reduction (TSR) is a common organic–inorganic interaction, which is in close association with the carbon cycle in sedimentary basins and metal sulfide precipitation in Mississippi Valley-type deposits. However, the reaction pathway and mechanism of TSR need further investigation, mainly due to the complex sulfur species involved in this reaction. Here we applied in situ Raman spectroscopy to disclose the stepwise transformation from sulfate to sulfide and the reaction kinetics in the CH4-Na2SO4/MgSO4/H2SO4-H2O systems at elevated temperatures and pressures. Our results indicate that sulfate is transformed to H2S through a series of reduction and disproportionation reactions. Once dissolved H2S reaches a certain concentration, it reacts with sulfate to form intermediate valence sulfur species (S0 and S3−), which quickly oxidize methane to generate CO2 and H2S. The formation of S3− and S0 is responsible for the autocatalytic effect in TSR. The sulfur speciation significantly affects the reaction kinetics, which could be divided into three stages based on the in situ observations. Extrapolated kinetic data show that TSR could proceed fast under the catalysis of H2S, and the half-life of methane is ∼7.10 million years at 200 °C. Subsequent numerical modeling strongly supports that in situ sulfate reduction could provide sufficient reduced sulfur for the formation of giant Mississippi Valley-type deposits, thus serving as an efficient mineralizing mechanism.

Mechanisms of the Gewald Synthesis of 2-Aminothiophenes from Elemental Sulfur.

The Gewald reaction is a well-established one-pot method to access 2-aminothiophenes from carbonyl compounds, activated acetonitriles, and elemental sulfur. To elucidate the reaction's poorly understood mechanism, with regard to the decomposition of sulfur and polysulfide intermediates, we have performed a comprehensive computational study using density functional theory (DFT) calculations at the M06-2X (or ωB97X-D)/aug-cc-pV(T + d)Z/SMD(C2H5OH) level of theory. The results show that the reaction is initiated by a Knoevenagel-Cope condensation, followed by opening of the elemental sulfur, leading to polysulfide formation. The polysulfide intermediates can interconvert and decompose using various mechanisms including unimolecular cyclization, nucleophilic degradation, and scrambling. Protonation of the polysulfides changes their electrophilic behavior and provides a kinetically favorable pathway for their decomposition. This protonation-induced intermolecular degradation is feasible for polysulfides of all lengths, but unimolecular decomposition is kinetically favored for long polysulfides (≥6 sulfur atoms). None of the pathways provide any thermodynamic benefit due to the lack of resonance-stabilized leaving group, and a complex equilibrium of polysulfides of all lengths is expected in solution. Cyclization of the monosulfide with aromatization to the thiophene product is the only driving force behind the reaction, funneling all of the various intermediates into the observed product in a thermodynamically controlled process.

Insight into the effects of gas molecules-adsorbed on 2D-FeS2: A DFT study

Lithium-sulfur (Li-S) batteries are especially competitive in the energy sector due to their excellent performances, like preferable energy density and economic benefits. Studying the adsorption of gas molecules on electrode materials has potential engineering significance for Li-S batteries since they have a highly osmotic potential, which causes unavoidable damage to batteries. In this work, the adsorption phenomenon of common gas molecules (H2O, N2, H2, CO2, and O2) on the two-dimensional pyrite (2D-FeS2) cathode material surface, as well as the effects on the electronic and electrochemical properties, were investigated by the first-principles calculations. The adsorption capabilities were estimated by adsorption energy and Mulliken population analysis. Simulation results demonstrated that whole adsorption energies were less than -1.0 eV and larger than -0.6 eV, which shows a physisorption nature. Among them, the O-S bond of O2/2D-FeS2 has the strongest strength. Electronic structure calculations suggested that 2D-FeS2 maintained good conductivity after gas molecules were adsorbed, achieving efficient transfer between electron, lithium, and sulfur intermediates. Additionally, ab initio molecular dynamics (AIMD) simulations showed that Li+ exhibits excellent diffusion performance and low activation energy at different temperatures. 2D-FeS2 still has a stable electrochemical working window (1.87 ∼ 2.47 V), while the theoretical open current voltage is damaged by gas molecule adsorption. Consequently, this work theoretically reveals the effect of gas molecules on the cathode materials for Li-S batteries, which has guide meaning for engineering.

A Volcano Correlation between Catalytic Activity for Sulfur Reduction Reaction and Fe Atom Count in Metal Center.

Sulfur reduction reaction (SRR) facilitates up to 16 electrons, which endows lithium-sulfur (Li-S) batteries with a high energy density that is twice that of typical Li-ion batteries. However, its sluggish reaction kinetics render batteries with only a low capacity and cycling life, thus remaining the main challenge to practical Li-S batteries, which require efficient electrocatalysts of balanced atom utilization and site-specific requirements toward highly efficient SRR, calling for an in-depth understanding of the atomic structural sensitivity for the catalytic active sites. Herein, we manipulated the number of Fe atoms in iron assemblies, ranging from single Fe atom to diatomic and triatomic Fe atom groupings, all embedded within a carbon matrix. This led to the revelation of a "volcano peak" correlation between SRR catalytic activity and the count of Fe atoms at the active sites. Utilizing operando X-ray absorption and X-ray diffraction spectroscopies, we observed that polysulfide adsorption-desorption and electrochemical conversion kinetics varied up and down with the incremental addition of even a single iron atom to the catalyst's metal center. Our results demonstrate that the metal center with exactly two iron atoms represents the optimal configuration, maximizing atom utility and adeptly handling the conversion of varied intermediate sulfur species, rendering the Li-S battery with a high areal capacity of 23.8 mAh cm-2 at a high sulfur loading of 21.8 mg cm-2. Our results illuminate the pivotal balance between atom utilization and site-specific requirements for optimal electrocatalytic performance in SRR and diverse electrocatalytic reactions.

Trends in estuarine pyrite formation point to an alternative model for Paleozoic pyrite burial

The early Paleozoic Era (∼540–420 Ma) was an interval of profound biogeochemical changes including increasing oxygen (O2) and the onset of bioturbation (sediment mixing by animals). It is hypothesized that incipient bioturbation caused a monotonic decrease in sedimentary burial of pyrite (FeS2), which would have slowed atmospheric O2 accumulation. However, pyrite accumulation can exhibit complex responses to dynamic, low-O2 environmental conditions. To assess pyrite burial in a potential modern analogue to early Paleozoic environments, we collected sediment cores from the Chesapeake Bay, an estuary with multiple gradients in sulfate concentration, hypoxia intensity, organic carbon flux and lability, and bioturbation. Results indicate that pyrite accumulation is maximized not under strong sulfate depletion in highly reducing sediments, but rather in sediments that occupy the mid-range of sulfate–chloride ratios. This probably occurs through efficient replenishment of pore water sulfate and/or through the generation of sulfur redox intermediates, which promote pyrite formation via the polysulfide reaction pathway. In light of these results and in contrast to earlier models, we hypothesize that mild early Paleozoic bioturbation temporarily increased pyrite burial efficiency by stimulating higher sulfate reduction rates and increasing sedimentary sulfide retention. Compiled sulfur and carbon data from a geochemical database indicate that median sulfur-carbon ratios of fine-grained marine siliciclastic rocks increased from the Ediacaran through the Ordovician, then decreased and became much less variable from the Silurian onward. Thus, the Cambrian and Ordovician Periods may constitute a distinct interval of the Proterozoic-Phanerozoic transition in which bioturbation temporarily accelerated O2 buildup. This transition probably ended in the Silurian, when pO2 rose to sufficient levels to homogenize sedimentary carbon–sulfur cycling.

Mechanism and structural dynamics of sulfur transfer during de novo [2Fe-2S] cluster assembly on ISCU2

Maturation of iron-sulfur proteins in eukaryotes is initiated in mitochondria by the core iron-sulfur cluster assembly (ISC) complex, consisting of the cysteine desulfurase sub-complex NFS1-ISD11-ACP1, the scaffold protein ISCU2, the electron donor ferredoxin FDX2, and frataxin, a protein dysfunctional in Friedreich’s ataxia. The core ISC complex synthesizes [2Fe-2S] clusters de novo from Fe and a persulfide (SSH) bound at conserved cluster assembly site residues. Here, we elucidate the poorly understood Fe-dependent mechanism of persulfide transfer from cysteine desulfurase NFS1 to ISCU2. High-resolution cryo-EM structures obtained from anaerobically prepared samples provide snapshots that both visualize different stages of persulfide transfer from Cys381NFS1 to Cys138ISCU2 and clarify the molecular role of frataxin in optimally positioning assembly site residues for fast sulfur transfer. Biochemical analyses assign ISCU2 residues essential for sulfur transfer, and reveal that Cys138ISCU2 rapidly receives the persulfide without a detectable intermediate. Mössbauer spectroscopy assessing the Fe coordination of various sulfur transfer intermediates shows a dynamic equilibrium between pre- and post-sulfur-transfer states shifted by frataxin. Collectively, our study defines crucial mechanistic stages of physiological [2Fe-2S] cluster assembly and clarifies frataxin’s molecular role in this fundamental process.

Iron Molybdenum Sulfide‐Supported Ultrafine Ru Nanoclusters for Robust Sulfion Degradation‐Assisted Hydrogen Production

AbstractElectrocatalytic hydrogen evolution and (S2−) recycling present promising strategies for cost‐effective hydrogen production and simultaneous removal of environmental pollutants. However, the advancement of this technology is hindered by the limited availability of affordable, efficient, and stable catalysts. Herein, the study synthesizes ultrafine ruthenium (Ru) nanoclusters on a substrate of iron molybdenum sulfide (FeMo‐S) nanosheets, creating a new heterointerface catalyst (FeMo‐S/Ru) for the hydrogen evolution reaction (HER) and sulfion oxidation reaction (SOR). Experimental and theoretical calculations suggest that strong electron interactions between Ru nanoclusters and FeMo‐S substrate, optimizing *H adsorption and promoting HER activity on one side while facilitating the production and adsorption of sulfur intermediates on the other side, effectively catalyzing SOR. Additionally, the assembled electrocatalytic coupling system with FeMo‐S/Ru displays an ultralow cell voltage of 0.57 V at 100 mA cm−2, achieving high Faradaic efficiencies (>96%) for H2 production, while also exhibiting remarkable durability over 1 month (838 h). This work paves the way for the development of highly efficient and durable supported catalysts, enabling energy‐saving hydrogen production and environmentally friendly sulfion recycling.

Reaction mechanisms and diagnostic mineralogy of intertidal steel corrosion: An X-ray photoelectron spectroscopy study

The products of intertidal and super tidal (splash zone) corrosion on steel piles have been characterised at 3 UK sites with contrasting environmental conditions in order to determine corrosion reaction mechanism and if a common mechanism for accelerated low water corrosion occurs across sites. Intertidal corrosion samples at Shoreham and Newhaven ports show an internal composition of iron mono- and bi-sulphide, with intermediate sulphur oxidation state compounds, and an outer surface dominated by iron oxides and oxyhydroxides with a component of iron sulphates. The FTIR spectra are characteristic of sulphate green rust. In contrast, samples from Southend have all sulphur species below detection levels and are dominated by iron oxides and oxyhydroxides. Carbon binding energy spectra are consistent with the development of biofilms at all sites except for a splash zone sample at Southend. The results demonstrate a common mechanism for ALWC at Newhaven and Shoreham, involving the action of sulphate-reducing bacteria generating iron sulphides on the steel surface. These are subsequently oxidised to produce sulphate green rust, which may in turn oxidise to produce lepidocrocite. At Southend differences in environment are inferred to restrict the activity of sulphate reducing bacteria, resulting in direct oxidation of steel to generate iron oxyhydroxide gels, which subsequently recrystallise, dehydrate and oxidise to goethite, magnetite and ultimately hematite in both splash zone and intertidal samples. The multi-technique approach used here characterises the full range of corrosion products.

Solvation-property relationship of lithium-sulphur battery electrolytes

The Li-S battery is a promising next-generation battery chemistry that offers high energy density and low cost. The Li-S battery has a unique chemistry with intermediate sulphur species readily solvated in electrolytes, and understanding their implications is important from both practical and fundamental perspectives. In this study, we utilise the solvation free energy of electrolytes as a metric to formulate solvation-property relationships in various electrolytes and investigate their impact on the solvated lithium polysulphides. We find that solvation free energy influences Li-S battery voltage profile, lithium polysulphide solubility, Li-S battery cyclability and the Li metal anode; weaker solvation leads to lower 1st plateau voltage, higher 2nd plateau voltage, lower lithium polysulphide solubility, and superior cyclability of Li-S full cells and Li metal anodes. We believe that relationships delineated in this study can guide the design of high-performance electrolytes for Li-S batteries.

Chamber studies of OH + dimethyl sulfoxide and dimethyl disulfide: insights into the dimethyl sulfide oxidation mechanism.

The oxidation of dimethyl sulfide (DMS) in the marine atmosphere represents an important natural source of non-sea-salt sulfate aerosol, but the chemical mechanisms underlying this process remain uncertain. While recent studies have focused on the role of the peroxy radical isomerization channel in DMS oxidation, this work revisits the impact of the other channels (OH addition and OH abstraction followed by bimolecular RO2 reaction) on aerosol formation from DMS. Due to the presence of common intermediate species, the oxidation of dimethyl sulfoxide (DMSO) and dimethyl disulfide (DMDS) can shed light on these two DMS reaction channels; they are also both atmospherically relevant species in their own right. This work examines the OH oxidation of DMSO and DMDS, using chamber experiments monitored by chemical ionization mass spectrometry and aerosol mass spectrometry to study the full range of sulfur-containing products across a range of NO concentrations. The oxidation of both compounds is found to lead to rapid aerosol formation (which does not involve the intermediate formation of SO2), with a substantial fraction (14%-47 % S yield for DMSO and 5 %-21 % for DMDS) of reacted sulfur ending up in the particle phase and the highest yields observed under elevated NO conditions. Aerosol is observed to consist mainly of sulfate, methanesulfonic acid, and methanesulfinic acid. In the gas phase, the NOx dependence of several products, including SO2 and S2-containing organosulfur species, suggest reaction pathways not included in current mechanisms. Based on the commonalities with the DMS oxidation mechanism, DMSO and DMDS results are used to reconstruct DMS aerosol yields; these reconstructions roughly match DMS aerosol yield measurements from the literature but differ in composition, underscoring remaining uncertainties in sulfur chemistry. This work indicates that both the abstraction and addition channels contribute to rapid aerosol formation from DMS and highlights the need for more study into the fate of small sulfur radical intermediates (e.g., CH3S, CH3SO2, and CH3SO3) that are thought to play central roles in the DMS oxidation mechanism.

Chemo- and bio-stratigraphic constraints on Cretaceous-Paleocene biotic turnover in the southern Tethys low-oxygen margin, Egypt

The late Cretaceous-Danian (K-Pg) organic-rich sequence is a global archive that witnessed abrupt paleo-condition changes during a high sea-level. In Egypt, this sequence is present in the Duwi and Dakhla formations as an E-W belt from the Red Sea to the Western Desert. We analyzed elemental and isotopic distributions in an age-constrained core from the Quseir area to understand paleoclimatic and paleoenvironmental factors influencing its deposition. Calcareous nannofossil and the chemical index of alteration (CIA) confirm a global cooling trend during the late Cretaceous, with two warming episodes indicating early phases of the Deccan volcanism. The Danian stage experienced a warm climate and intense chemical weathering. Mo-U enrichment factors covariation suggest deposition under oxygen-deficient conditions with evident watermass restrictions. High-productivity-indicating taxa were more abundant in Danian strata than in late Cretaceous strata, consistent with organic carbon characteristics. The δ13COrg-δ15N data show temporal heterogeneity due to organic matter type, redox conditions, preservation, stratigraphic condensation, and recycling of isotopically-light CO2. The negative δ13COrg shift around the K-Pg transition is globally correlative. Dynamic pyrite δ34S distribution resulted from variation in riverine influx, degree of pore-water openness, sulfate reduction rate, and diagenetic disproportionation of sulfur intermediates. Generally, radiogenic 187Os/188Os values were observed that were seemingly influenced by continental weathering and subsequent runoff influx of 187Os/188Os under a greenhouse climate. A positive 187Os/188Os shift to 3.68 (187Os/188Osi of 0.74) occurred at the onset of the Dakhla organic-rich spike. However, without a precise correlative stratigraphic framework, a global or regional seawater isotopic shift cannot be confirmed. We suggest that temporal variations in organic matter composition, redox, watermass conditions, and isotope fractionation of the K-Pg sequence in the study area were driven by discrepancies in climate, sea-level, and tectonic uplift. Further integrated approaches are needed to explore the geospheric drivers of this organic-rich sequence in time-equivalent sections.

Abiotic aerobic oxidation pathways of stibnite revealed by oxygen and sulfur isotope systematics of sulfate

The environmental threat posed by stibnite is an important geoenvironmental issue of current concern. To better understand stibnite oxidation pathways, aerobic abiotic batch experiments were conducted in aqueous solution with varying δ18OH2O value at initial neutral pH for different lengths of time (15-300 days). The sulfate oxygen and sulfur isotope compositions as well as concentrations of sulfur and antimony species were determined. The sulfur isotope fractionation factor (Δ34SSO4-stibnite) values decreased from 0.8‰ to -2.1‰ during the first 90 days, and increased to 2.6‰ at the 180 days, indicating the dominated intermediate sulfur species such as S2O32−, S0, and H2S (g) involved in Sb2S3 oxidation processes. The incorporation of O into sulfate derived from O2 (∼100%) indicated that the dissociated O2 was only directly adsorbed on the stibnite-S sites in the initial stage (0-90 days). The proportion of O incorporation into sulfate from water (27%-52%) increased in the late stage (90-300 days), which suggested the oxidation mechanism changed to hydroxyl attack on stibnite-S sites promoted by nearby adsorbed O2 on stibnite-Sb sites. The exchange of oxygen between sulfite and water may also contributed to the increase of water derived O into SO42−. The new insight of stibnite oxidation pathway contributes to the understanding of sulfide oxidation mechanism and helps to interpret field data.