The adsorption of sulfur by microporous materials

The sorption of sulfur by the zeolites NaX (= 13X) and CaA (= 5A) and an activated charcoal prepared from sugar was investigated at temperatures between 150 and 350°C and relative sulfur pressures between 10−4 and 10−1. The adsorbate-adsorbate interaction indicated by the S-shaped isotherm for the zeolite NaX points to physical or chemical interaction of sulfur molecules in neighboring supercages. In CaA adsorbate-adsorbate interaction between sulfur species in different supercages is negligible. Below 200°C the rate of sulfur uptake by the zeolite CaA is determined by the diffusion rate of a sulfur species through the zeolitic framework. In activated charcoal a strong adsorbate-adsorbent interaction is present and part of the sulfur is chemisorbed at 350°C. The differences in the density of the adsorbed sulfur determined with three different methods indicate that even at full saturation of the micropore volume with sulfur, there is still some residual adsorption volume

Polyisoprene Captured Sulfur Nanocomposite Materials for High-Areal-Capacity Lithium Sulfur Battery

A polyisoprene-sulfur (PIPS) copolymer and nano sulfur composite material (90 wt % sulfur) is synthesized through inverse vulcanization of PIP polymer with micrometer-sized sulfur particles for high-areal-capacity lithium sulfur batteries. The polycrystalline structure and nanodomain nature of the copolymer are revealed through high-resolution transmission electron microscopy (HRTEM). PIP polymer is also used as binders for the electrode to further capture the dissovlved polysulfides. A high areal capacity of ca. 7.0 mAh/cm2 and stable cycling are achieved based on the PIPS nanosulfur composite with a PIP binder, crucial to commercialization of lithium sulfur batteries. The chemical confinement both at material and electrode level alleviates the diffusion of polysulfides and the shuttle effect. The sulfur electrodes, both fresh and cycled, are analyzed through scanning electron microscopy (SEM). This approach enables scalable material production and high sulfur utilization at the cell level

A new study of an old sink of sulfur in hot molecular cores: the sulfur residue

Sulfur appears to be depleted by an order of magnitude or more from its elemental abundance in star-forming regions. In the last few years, numerous observations and experiments have been performed in order to to understand the reasons behind this depletion without providing a satisfactory explanation of the sulfur chemistry towards high-mass star-forming cores. Several sulfur-bearing molecules have been observed in these regions, and yet none are abundant enough to make up the gas-phase deficit. Where, then, does this hidden sulfur reside? This paper represents a step forward in our understanding of the interactions among the various S-bearing species. We have incorporated recent experimental and theoretical data into a chemical model of a hot molecular core in order to see whether they give any indication of the identity of the sulfur sink in these dense regions. Despite our model producing reasonable agreement with both solid-phase and gas-phase abundances of many sulfur-bearing species, we find that the sulfur residue detected in recent experiments takes up only ~6 per cent of the available sulfur in our simulations, rather than dominating the sulfur budget.Comment: 13 pages, 6 colourful figures, accepted by MNRA

Geochemistry of reduced inorganic sulfur, reactive iron, and organic carbon in fluvial and marine surface sediment in the Laizhou Bay region, China

Understanding the geochemical cycling of sulfur in sediments is important because it can have implications for both modern environments (e.g., deterioration of water quality) and interpretation of the ancient past (e.g., sediment C/S ratios can be used as indicators of palaeodepositional environment). This study investigates the geochemical characteristics of sulfur, iron, and organic carbon in fluvial and coastal surface sediments of the Laizhou Bay region, China. A total of 63 sediment samples were taken across the whole Laizhou Bay marine region and the 14 major tidal rivers draining into it. Acid volatile sulfur, chromium (II)-reducible sulfur and elemental sulfur, total organic carbon, and total nitrogen were present in higher concentrations in the fluvial sediment than in the marine sediment of Laizhou Bay. The composition of reduced inorganic sulfur in surface sediments was dominated by acid volatile sulfur and chromium (II)-reducible sulfur. In fluvial sediments, sulfate reduction and formation of reduced inorganic sulfur were controlled by TOC and reactive iron synchronously. High C/S ratios in the marine sediments indicate that the diagenetic processes in Laizhou Bay have been affected by rapid deposition of sediment from the Yellow River in recent decades

The role of sulfur trapped in micropores in the catalytic partial oxidation of hydrogen sulfide with oxygen

The catalytic oxidation of hydrogen sulfide into sulfur with molecular oxygen has been studied in the temperature range 130–200 °C. Active carbon, molecular sieve 13X and liquid sulfur were used as catalysts. Sulfur is adsorbed in the micropores (3 < r < 40 Å) of the catalysts. Experiments with a surface of liquid sulfur demonstrated that sulfur is a catalyst for H2S oxidation.\ud \ud This catalytic function reflects itself in the fact that H2S oxidation rate showed a maximum as a function of the amount of sulfur present in the pores of active carbon and molecular sieve 13X. The kinetics of the reaction and the activation energy are equal on catalysts of different chemical composition.\ud \ud The mechanism of the catalysis by sulfur is discussed as well as the function of traces of iron oxide, present in most catalysts

Coal desulfurization process

A method for chlorinolysis of coal is an organic solvent at a moderate temperautre and atmospheric pressure has been proven to be effective in removing sulfur, particularly the organic sulfur, from coal. Chlorine gas is bubbled through a slurry of moist coal in chlorinated solvent. The chlorinated coal is separated, hydrolyzed and the dechlorinated. Preliminary results of treating a high sulfutr (4.77%S) bituminous coal show that up to 70% organic sulfur, 90% hyritic sulfur and 76% total sulfur can be removed. The treated coal is dechlorinated by heating at 500 C. The presence of moisture helps to remove organic sulfur

UV-light-driven prebiotic synthesis of iron–sulfur clusters

Iron–sulfur clusters are ancient cofactors that play a fundamental role in metabolism and may have impacted the prebiotic chemistry that led to life. However, it is unclear whether iron–sulfur clusters could have been synthesized on prebiotic Earth. Dissolved iron on early Earth was predominantly in the reduced ferrous state, but ferrous ions alone cannot form polynuclear iron–sulfur clusters. Similarly, free sulfide may not have been readily available. Here we show that UV light drives the synthesis of [2Fe–2S] and [4Fe–4S] clusters through the photooxidation of ferrous ions and the photolysis of organic thiols. Iron–sulfur clusters coordinate to and are stabilized by a wide range of cysteine-containing peptides and the assembly of iron–sulfur cluster-peptide complexes can take place within model protocells in a process that parallels extant pathways. Our experiments suggest that iron–sulfur clusters may have formed easily on early Earth, facilitating the emergence of an iron–sulfur-cluster-dependent metabolism

Organic sulfur: a spatially variable and understudied component of marine organic matter

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Longnecker, K., Oswald, L., Soule, M. C. K., Cutter, G. A., & Kujawinski, E. B. Organic sulfur: a spatially variable and understudied component of marine organic matter. Limnology and Oceanography Letters, (2020), doi:10.1002/lol2.10149.Sulfur (S) is a major heteroatom in organic matter. This project evaluated spatial variability in the concentration and molecular‐level composition of organic sulfur along gradients of depth and latitude. We measured the concentration of total organic sulfur (TOS) directly from whole seawater. Our data reveal high variability in organic sulfur, relative to established variability in total organic carbon or nitrogen. The deep ocean contained significant amounts of organic sulfur, and the concentration of TOS in North Atlantic Deep Water (NADW) decreased with increasing age while total organic carbon remained stable. Analysis of dissolved organic matter extracts by ultrahigh resolution mass spectrometry revealed that 6% of elemental formulas contained sulfur. The sulfur‐containing compounds were structurally diverse, and showed higher numbers of sulfur‐containing elemental formulas as NADW moved southward. These measurements of organic sulfur in seawater provide the foundation needed to define the factors controlling organic sulfur in the global ocean.We thank Catherine Carmichael, Winifred Johnson, and Gretchen Swarr for assistance with sample collection and processing, and Joe Jennings for the analysis of inorganic nutrients. The help of the captain and crew of the R/V Knorr and the other cruise participants during the “DeepDOM” cruise is appreciated. Two anonymous reviewers and Patricia Soranno provided thorough comments that greatly improved the manuscript. The ultrahigh resolution mass spectrometry samples were analyzed at the WHOI FT‐MS Users' Facility that is funded by the National Science Foundation (grant OCE‐0619608) and the Gordon and Betty Moore Foundation (GMBF1214). This project was funded by NSF grants OCE‐1154320 (to EBK and KL), the W.M. Marquet Award (to KL), and OCE‐1435708 (to GAC). The authors declare no conflicts of interest