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Controls on Highly Siderophile Element Concentrations in Martian Basalt: Sulfide Saturation and Under-Saturation

Highly siderophile elements (HSE; Re, Au and the platinum group elements) in shergottites exhibit a wide range from very high, similar to the terrestrial mantle, to very low, similar to sulfide saturated mid ocean ridge basalt (e.g., [1]). This large range has been difficult to explain without good constraints on sulfide saturation or under-saturation [2]. A new model for prediction of sulfide saturation places new constraints on this problem [3]. Shergottite data: For primitive shergottites, pressure and temperature estimates are between 1.2-1.5 GPa, and 1350-1470 C [4]. The range of oxygen fugacities is from FMQ-2 to IW, where the amount of Fe2O3 is low and thus does not have a significant effect on the S saturation values. Finally, the bulk compositions of shergottites have been reported in many recent studies (e.g., [5]). All of this information will be used to test whether shergottites are sulfide saturated [3]. Modeling values and results: The database for HSE partition coefficients has been growing with many new data for silicates and oxides [6-8] to complement a large sulfide database [9- 11]. Combining these data with simple batch melting models allows HSE contents of mantle melts to be estimated for sulfide-bearing vs. sulfide-free mantle. Combining such models with fractional crystallization modeling (e.g., [12]) allows HSE contents of more evolved liquids to be modeled. Most primitive shergottites have high HSE contents (and low S contents) that can be explained by sulfide under-saturated melting of the mantle. An exception is Dhofar 019 which has high S contents and very low HSE contents suggesting sulfide saturation. Most evolved basaltic shergottites have lower S contents than saturation, and intermediate HSE contents that can be explained by olivine, pyroxene, and chromite fractionation. An exception is EET A79001 lithology B, which has very low HSE contents and S contents higher than sulfide saturation values . evidence for sulfide saturation during late fractional crystallization. These results show that shergottite HSE contents are controlled by silicates, oxides, and sulfides. In addition, the mantle producing the most primitive shergottites did not contain near chondritic relative ratios of the HSEs like the terrestrial mantle, and did not experience a late chondritic veneer.

Righter, Kevin↗

Iron-Nickel Sulfide Compositional Ranges in CM Chondrites: No Simple Plan

Iron-nickel sulfides are found in most or all solar system environments, and are probably the only minerals found in all extraterrestrial materials on hand. Despite this ubiquity, they have only just begun the attention they deserve. The most common Fe-Ni sulfides in chondrites are troilite (FeS), pyrrhotite (Fe(1-x)S) and pentlandite (Fe,Ni)9S8. Troilite is believed to have resulted from sulfidation of metal (Fe-Ni) grains in an H2S-containing environment. Pyrrhotite is produced when friable troilite grains, which are exfoliated from the metal nucleus, are submitted to continued sulfidation. Some asteroids are known to have experienced aqueous alteration, forming products including new generations of sulfides (pyrrhotite and pentlandite). Pentlandite in particular is known to form during such alteration. However, experimental work by Lauretta has indicated that pentlandite may also have been formed during the initial sulfidation process, due to the faster diffusion rate of nickel into the forming sulfide, as compared to iron. Finally, there is considerable evidence for a family of phases intermediate between pyrrhotite and pentlandite, following the trend of the high temperature monosulfide solid solution, something not encountered in terrestrial rocks. Each sulfide has its own particular stability conditions, which have been determined for most phases. The long-term objective of our research is to characterize sulfides in chondritic materials in order to better establish the conditions under which they formed, and the subsequent processes they experienced. Ultimately, it will be possible to infer whether the sulfides in the chondrites were formed in the solar nebula or on asteroids, and if formed on the asteroids, deduce how much alteration has occurred there. Here we explore the relationships between the finest grain size portions of carbonaceous chondrites, these being matrix and chondrule rims; fine-grained materials are the most sensitive to their environment. This abstract is one of a series reporting results for chondrites, earlier work reported results for a much more limited set of CMs, as well as for CVs and CIs.

Zolensky, Michael↗

Calcium and Magnesium Distribution Between Sulfide and Silicate Melts: Thermodynamic Modeling and Insights into Mercury's Mantle-Crust Differentiation

Mercury stands out as the terrestrial planet with the lowest degree of oxidation among all planets of our solar system. It is characterized by a high abundance of sulfur, which is expected to replace oxygen in silicate melts. This sulfur enrichment could lead to sulfide saturation in its mantle, potentially resulting in the formation of sulfides rich in calcium and magnesium. Utilizing experimental data from the literature, we constructed a thermodynamic model to explore the partitioning of calcium and magnesium between sulfide and silicate melts. This model aims to improve our comprehension of the chemical equilibria driving the process of mantle-crust differentiation on Mercury. Our models indicate that increased temperature, decreased pressure, and low concentrations of iron, oxygen, and carbon within the sulfide phase, along with low sulfur concentrations in the silicate phase, favor calcium’s partitioning into the sulfide. Additionally, magnesium partitioning into the sulfide melt is favored with decreased pressure, decreased temperature, low concentrations of iron and calcium within the sulfide, and low concentrations of sulfur within the silicate. Our results suggest that up 9.4% and 5.6% Ca and Mg, respectively, can be present in sulfides equilibrated with sulfide-saturated silicate melts during mantle-crust differentiation. Further investigation will focus on the distribution of sulfide phases within the mantle and crust to better constrain Mercury’s internal structure.

Taylor McCombs↗

Electrochemical sulfate production from sulfide-containing wastewaters and integration with electrochemical nitrogen recovery

Electrochemical methods can help manage sulfide in wastewater, which poses environmental and health concerns due to its toxicity, malodor, and corrosiveness. In addition, sulfur could be recovered as fertilizer and commodity chemicals from sulfide-containing wastewaters. Wastewater characteristics vary widely among wastewaters; however, it remains unclear how these characteristics affect electrochemical sulfate production. Here, in this study, we evaluated how four characteristics of influent wastewaters (electrolyte pH, composition, sulfide concentration, and buffer strength) affect sulfide removal (sulfide removal rate, sulfide removal efficiency) and sulfate production metrics (sulfate production rate, sulfate production selectivity). We identified that electrolyte pH (3 × difference, i.e., 25.1 to 84.9 μM h –1 in average removal rate within the studied pH range) and sulfide concentration (16 × difference, i.e., 82.1 to 1347.2 μM h –1 in average removal rate) were the most influential factors for electrochemical sulfide removal. Sulfate production was most sensitive to buffer strength (6 × difference, i.e., 4.4 to 27.4 μM h –1 in average production rate) and insensitive to electrolyte composition. Together, these results provide recommendations for the design of wastewater treatment trains and the feasibility of applying electrochemical methods to varying sulfide-containing wastewaters. In addition, we investigated a simultaneous multi-nutrient (sulfur and nitrogen) process that leverages electrochemical stripping to further enhance the versatility and compatibility of electrochemical nutrient recovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Additional Trials & Tribulations in Synthesizing a Sulfide Standard

Well-characterized sulfide reference materials that can serve as matrix-matched calibrants for in-situ trace element analyses via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remain elusive. Here, we describe the creation an in-house sulfide standard at NASA JSC that will be used to measure siderophile and chalcophile trace elements in low pressure experimental products, specifically pentlandite ([FeNi]9S8) and pyrrhotite ([FeNi]1-xS), as well as natural sulfides in terrestrial and meteoritic mineral assemblages. Recent methods in creating a homogenous sulfide standard include pressed pellets, synthesized chips, or fused glass [e.g. 1-3]. Other studies, however, have had success in forming homogenous FeS standards via synthesization methods [e.g. 4-6]. We present a variation of the method described in [4], in which we create a pyrrhotite standard doped with a variety of trace elements (Zn, As, Se, Mo, Ru, Rh, Pd, Sn, Sb, Te, W, Os, Ir, Pt, Au) at ~10-40 ppm and Cu at ~200 ppm. Sulfide compositions were constructed using Fe and Ni metal and elemental sulfur powders. Trace elements were added to elemental sulfur from Atomic Absorption Spectroscopy (AAS) elemental standards as either nitrate or chloride solutions to prevent oxidation of the metal powders. The dried sulfur mixture was mixed with Fe and Ni powders and mechanically mixed before two aliquots were placed in separate SiO2 tubes. Each tube was held under vacuum for ~30 minutes, sealed under vacuum, and then heated at 800C for 48 hours. Like [4], the synthesis products were composed of pourous sulfide crystals. Major element analyses of both experimental aliquots, collected using an Electron Probe Microanalyser (EPMA), yield indistinguishable major element compositions (uncertainties in 2SE & 2RSE[%]), with an average of 57.90  0.09 (0.16 %), 4.95  0.03 (0.55 %), and 39.70  0.14 (0.34 %), for Fe, Ni, and S, respectively. Trace element data were measured using a Photon Machines 193nm laser ablation system coupled to a Thermo-Scientific Element-XR ICP-MS. Spot sizes were limited to 50 μm due to the porous nature of the sulfide target material. Trace element abundances, normalized to Fe as an internal standard, were also found to be homogenous between the two aliquots, with weighted mean 2RSE (%) values of <3.0 for all trace elements. Synthesized products were re-powdered and absolute concentrations measured via solution ICP-MS. Although the sulfide appears to be homogenous, sintering experiments will be performed to more closely match the standard density to natural sulfides and minimize differences in ablation behavior. Improved density also allows for higher sensitivity (i.e. more compact target material) and larger spot sizes or traverses, as void space is eliminated. Additional major and trace element analyses on the products of the sintering experiments will be undertaken.

Jacob B Setera↗

Behaviour of cadmium isotopes in sulfidic waters and sediments of the Black Sea: Implications for global cadmium cycling and the application of cadmium isotopes as a paleo-oceanographic proxy

The cadmium isotope system has found use as a tracer for biological productivity, redox and organic carbon burial in the oceans. There are, however, very few observational constraints on Cd isotopic behaviour in modern sulfidic marine conditions, limiting our understanding of the modern Cd cycle, and our ability to use Cd isotope measurements of ancient sedimentary deposits as a paleoceanographic proxy. Here we study the behaviour of dissolved Cd in the water column of the Black Sea and its incorporation into sediments on the basin floor. The isotopic composition of dissolved Cd in the upper ∼50 m of the Black Sea water column is controlled by a combination of biological uptake and regeneration along with mixing of river water and Mediterranean seawater. Cadmium declines to <2 % of its peak subsurface concentration within the zone of nitrate-reduction but above the sulfide chemocline. The isotopic composition of dissolved Cd below the sulfide chemocline evolves in a manner that is consistent with experimental Cd sulfide fractionation factors, providing field-based support for these earlier studies. In contrast, the stability of the dissolved Cd isotopic signature above the chemocline, despite a large reduction in dissolved Cd concentrations, is explained by diffusion towards the Cd-sulfide sink below the chemocline. Sediments accumulating in the deep Black Sea below the sulfide chemocline have isotopic compositions that are similar to dissolved Cd in its near-surface aqueous concentration maximum. Sediments accumulating at shallower depths have lighter isotopic compositions that are likely affected by non-sulfidic burial pathways mediated by macrofaunal mixing and diagenesis of shallow burial phases. Our study shows that the isotopic composition of bulk sediments accumulating under sulfidic conditions is similar to dissolved Cd in the upper water column, supporting its use as a paleo-chemical proxy for ancient seawater as long as basin-scale controls on open ocean seawater sources are considered. We show that Cd burial in the deep Black Sea, predominantly as CdS, accounts for ∼0.5–15 % of total annual Cd burial in the global ocean.

Biogeochemical cycles↗

Influence of temperature and the role of chromium on the kinetics of sulfidation of 310 stainless steel

The sulfidation of 310 stainless steel was studied over the temperature range from 910 K to 1285 K. By adjusting the ratio of hydrogen sulfide, variations in sulfur potential were obtained. The effect of temperature on sulfidation was determined at three different sulfur potentials: 39/sqNm, 0.014/sqNm, and 0.00015/sqNm. All sulfide scales contained one or two surface layers in addition to a subscale. The second outer layer (OL-II), furthest from the alloy, contained primarily Fe-Ni-S. The first outer layer (OL-I), nearest the subscale, contained FE-Cr-S. The subscale consisted of sulfide inclusions in the metal matrix. At a given temperature and sulfur potential, the weight gain data obeyed the parabolic rate law after an initial transient period. The parabolic rate constants obtained at the sulfur potential of 39/sqNm did not show a break when the logarithm of the rate constant was plotted as a function of the inverse of absolute temperature. Sulfidation carried out at sulfur potentials below 0.02/sqNm, however, did show a break at 1145 K, which is termed as the transition temperature. This break was found to be associated with the changes which had occurred in the Fe:Cr ratio of OL-I. Below the transition temperature the activation energy was found to be approximately 125 kj/mole. Above the transition temperature the rate of sulfidation decreased with temperature but dependent on the Fe:Cr ratio in the iron-chromium-sulfide layers of the OL-I. A reaction mechanism consistent with the experimental results has been proposed.

Rao, D. B.↗

Early and Late Stage Metals and Sulfides in Diogenites

Diogenites are typically highly brecciated orthopyroxenites that contain 84-100 vol.% orthopyroxene. Common accessory minerals include olivine, chromite, Ca-pyroxene, plagioclase, silica, troilite and Fe-Ni metal. Metal and sulfides are minor phases in diogenites with an average abundance of < 1 vol.% and 0-2 vol.% respectively. However their presence is important, as they could provide information on T-fO2-fS2 conditions and the evolution of the diogenite parent magma during crystallization and/or later metamorphism. We have examined the occurrence of Fe-Ni metal and sulfides in thin sections of several diogenites including, Johnstown, Manegaon, Roda, Shalka, Bilanga, and Tatahouine using optical microscopy and the electron microprobe. Here, we describe three features of metals and sulfides that are common in most of these diogenites. These are: i) The widespread occurrence of pentlandite associated with copper and copper sulfide minerals; ii) Textural evidence that at least some of the metal and sulfide occurring interstitially between, and as inclusions within, orthopyroxene formed from an early immiscible sulfide-oxide liquid; iii) That this sulfide- oxide liquid subsequently fractionated into assemblages containing either Fe-Ni metal, troilite, and chromite or pentlandite, troilite, and copper-bearing sulfide.

Sideras, L. C.↗

The Formation and Chronology of the PAT 91501 Impact-Melt L-Chondrite with Vesicle-Metal-Sulfide Assemblages

The L chondrite Patuxent Range (PAT) 41 91501 is an 8.5-kg unshocked, homogeneous, igneous-textured impact melt that cooled slowly compared to other meteoritic impact melts in a crater floor melt sheet or sub-crater dike. We conducted mineralogical and tomographic studies of previously unstudied mm- to cm-sized metal-sulfide-vesicle assemblages and chronologic studies of the silicate host. Metal-sulfide clasts constitute about 1 vol.%, comprise zoned taenite, troilite and pentlandite, and exhibit a consistent orientation between metal and sulfide and of metal-sulfide contacts. Vesicles make up approximately 2 vol.% and exhibit a similar orientation of long axes. Ar-39-Ar-40 measurements date the time of impact at 4.461 +/- 0.008 Gyr B.P. Cosmogenic noble gases and Be-10 and Al-2l activities suggest a pre-atmospheric radius of 40-60 cm and a cosmic ray exposure age of 25-29 Myr, similar to ages of a cluster of L chondrites. PAT 91501 dates the oldest known impact on the L chondrite parent body. The dominant vesicle-forming gas was S2 (approximately 15-20 ppm), which formed in equilibrium with impact-melted sulfides. The meteorite formed in an impact melt dike beneath a crater, as did other impact melted L chondrites, such as Chico. Cooling and solidification occurred over approximately 2 hours. During this time, approximately 90% of metal and sulfide segregated from the local melt. Remaining metal and sulfide grains oriented themselves in the local gravitational field, a feature nearly unique among meteorites. Many of these metal sulfide grains adhered to vesicles to form aggregates that may have been close to neutrally buoyant. These aggregates would have been carried upward with the residual melt, inhibiting further buoyancy-driven segregation. Although similar processes operated individually in other chondritic impact melts, their interaction produced the unique assemblage observed in PAT 91501.

Benedix, G. K.↗

The Search for Interstellar Sulfide Grains

The lifecycle of sulfur in the galaxy is poorly understood. Fe-sulfide grains are abundant in early solar system materials (e.g. meteorites and comets) and S is highly depleted from the gas phase in cold, dense molecular cloud environments. In stark contrast, sulfur is essentially undepleted from the gas phase in the diffuse interstellar medium, indicating that little sulfur is incorporated into solid grains in this environment. It is widely believed that sulfur is not a component of interstellar dust grains. This is a rather puzzling observation unless Fe-sulfides are not produced in significant quantities in stellar outflows, or their lifetime in the ISM is very short due to rapid destruction. Fe sulfide grains are ubiquitous in cometary samples where they are the dominant host of sulfur. The Fe-sulfides (primarily pyrrhotite; Fe(1-x)S) are common, both as discrete 0.5-10 micron-sized grains and as fine (5-10 nm) nanophase inclusions within amorphous silicate grains. Cometary dust particles contain high abundances of well-preserved presolar silicates and organic matter and we have suggested that they should contain presolar sulfides as well. This hypothesis is supported by the observation of abundant Fe-sulfides grains in dust around pre- and post-main sequence stars inferred from astronomical spectra showing a broad 23 micron IR feature due to FeS. Fe-sulfide grains also occur as inclusions in bona fide circumstellar amorphous silicate grains and as inclusions within deuterium-rich organic matter in cometary dust samples. Our irradiation experiments show that FeS is far more resistant to radiation damage than silicates. Consequently, we expect that Fe sulfide stardust should be as abundant as silicate stardust in solar system materials.

Keller, Lindsay P.↗

Moisture Stability of Sulfide Solid-State Electrolytes

In this report we detail a comprehensive study on the moisture stability of sulfide solid-state electrolytes in dry room environments. Although sulfide SSEs have many favorable attributes, this class of materials suffers from poor stability with water. Sulfide SSEs react with water to form gaseous H 2 S and a variety of solid byproducts like Li 3 PO 4 and LiOH, which go on to increase the interfacial impedance of solid-state batteries. Lab-scale research typically utilizes gloveboxes with <1 ppm water, however, the large-scale manufacturing of Li-ion batteries occurs in –40°C dewpoint dry rooms with around 126 ppm water. Consequently, the moisture stability of sulfide SSEs must be addressed if the manufacture of solid-state batteries based on sulfide SSEs is to be scaled up. Here, we are the first to characterize the moisture stability of sulfide SSEs according to both H 2 S and the degradation of ionic conductivity at different moisture setpoints ranging from –76°C to –40°C dewpoint. A variety of different SSE compositions are studied; namely, (Li 2 S) 75 (P 2 S 5 ) 25 , (Li 2 S) 70 (P 2 S 5 ) 30 , (Li 2 O) 7 (Li 2 S) 68 (P 2 S 5 ) 25 , (Li 2 O) 7 (Li 2 S) 63 (P 2 S 5 ) 30 , and (Li 2 S) 75 (P 2 S 5 ) 25 + 20 mol% LiI. We find that moisture stability improves with 75 mol% Li2S modifier content and the introduction of a Li 2 O co-modifier. After a 30 min exposure in a –40°C dewpoint dry room environment we found that (Li 2 S) 75 (P 2 S 5 ) 25 + 20 mol% LiI powder generated 0.1 cc/g H 2 S and its ionic conductivity decreased by over 50%. However, when SSE powder was exposed as a slurry in a dodecane carrier the same SSE composition generated 0 cc/g H 2 S and its ionic conductivity only dropped by 14%. Our results show that sulfide SSEs have acceptable moisture stability when appropriately processed in a dry room environment.

25 ENERGY STORAGE↗

Formation Mechanisms, Crystal Structure, and Interfacial Reactivity of (Mixed) Metal Sulfide Nanoparticles Produced via Biological versus Abiotic Systems

The primary goals of this project were to understand the formation mechanisms and reactivity of mix-metal sulfide nanophases (Cu-Fe, Ni-Fe, Co-Fe sulfides) produced via biological and abiotic pathways that are relevant to low-temperature aqueous environments. These mix-metal sulfide nanophases have been identified in a range of natural and anthropogenic systems and are considered to play key roles in the biogeochemical cycling of elements, biomineralization, environmental remediation, resource recovery, eco-toxicity, and the origin and evolution of life. Using a comparative approach, we aimed to elucidate: (i) if these mix-metal sulfides tend to form nanoscale phases regardless of their formation pathways; (ii) what mechanisms are involved in the biological and abiotic crystallization processes; (iii) what phases form that have been otherwise expected; and (iv) if we can combine the experimental results with what we see and surmise from field studies to facilitate a more comprehensive understanding regarding the origin and biogeochemical roles of these mix-metal sulfides. Along a related pathway of electron transfer in nano-systems, in this case dealing with Fe-oxides instead of Fe-sulfides, we have continued to explore the reactions and solid products of heterogeneous catalytic oxidation of aqueous Mn(II) by dissolved oxygen in the presence of iron oxides (hematite) nanoparticles. The nano-Mn-oxides produced are known to be efficient sorbents of transition metal elements, including Cu, Ni, and Co studied in our sulfide work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetite-sulfide chondrules and nodules in CK carbonaceous chondrites - Implications for the timing of CK oxidation

CK carbonaceous chondrites contain rare (about 0.1 vol pct) magnetite-sulfide chondrules that range from about 240 to 500 microns in apparent diameter and have ellipsoidal to spheroidal morphologies, granular textures, and concentric layering. They resemble the magnetite-sulfide nodules occurring inside mafic silicate chondrules in CK chondrites. It seems likely that the magnetite-sulfide chondrules constitute the subset of magnetite-sulfide nodules that escaped as immiscible droplets from their molten silicate chondrule hosts during chondrule formation. The intactness of the magnetite-sulfide chondrules and nodules implies that oxidation of CK metal occurred before agglomeration. Hence, the pervasive silicate darkening of CK chondrites was caused by the shock mobilization of magnetite and sulfide, not metallic Fe-Ni and sulfide as in shock-darkened ordinary chondrites.

Rubin, Alan E.↗

Examining Metasomatism in Low fO2 Environments: Exploring Sulfidation Reactions in Various Planetary Bodies

Hydrothermal systems are common on Earth in a variety of tectonic environments and at different temperature and pressure conditions. These systems are commonly dominated by H2O, and they are responsible for element transport and the production of ore deposits. Unlike the Earth (fO2~FMQ), many other planetary bodies (e.g., Moon and asteroids) have fO2 environments that are more reduced (IW+/-2), and H2O is not the important solvent responsible for element transport. One example of a texture that could result from element transport and metasomatism, which appears to occur on numerous planetary bodies, is sulfide-silicate intergrowths. These subsolidus assemblages are interpreted to form as a result of sulfidation reactions from a S-rich fluid phase. The composition of fluids may vary within and among parent bodies and could be sourced from magmatic (e.g. Moon) or impact processes (e.g. HED meteorites and Moon). For example, it has been previously demonstrated on the Moon that the interaction of olivine with a hydrogen- and sulfur-bearing vapor phase altered primary mineral assemblages, producing sulfides (e.g. troilite) and orthopyroxene. Formation of these types of "sulfidation" assemblages can be illustrated with the following reaction: Fe2SiO4(ol) + 1/2 S(2 system) = FeS(troi)+ FeSiO3(opx) + 1/2 O2 system. The products of this reaction, as seen in lunar rocks, is a vermicular or "worm-like" texture of intergrown orthopyroxene and troilite. Regardless of the provenance of the S-bearing fluid, the minerals in these various planetary environments reacted in the same manner to produce orthopyroxene and troilite. Although similar textures have been identified in a variety of parent bodies, a comparative study on the compositions and the origins of these sulfide-silicate assemblages has yet to be undertaken. The intent of this study is to examine and compare sulfide-silicate intergrowths from various planetary bodies to explore their petrogenesis and examine the nature of low fO2 (IW+/-2) element migration and sulfidation reactions.

Srinivasan, P.↗

Molybdenum oxide and sulfide active sites for isobutane dehydrogenation with methanol as a probe molecule

Molybdenum oxides and sulfides are alternative catalysts for several reactions, including alkane dehydrogenation. Correlations have been developed between reactivity and structure, but it is difficult to compare different catalysts without determining numbers of active sites. Here, methanol temperature programmed surface reaction (TPSR) is applied to bulk MoS 2 and a series of supported molybdenum oxides and sulfides used for isobutane dehydrogenation. Rates and deactivation behavior are similar between supported molybdenum oxides and sulfides. Coking increases with loading and correlates well with the fraction of Mo-based CO 2 -forming sites from methanol TPSR. Normalizing isobutane dehydrogenation rates by formaldehyde-forming sites unifies rates over oxide and sulfide materials. Further, these measurements confirm earlier hypotheses that MoS 2 and higher loadings of oxides and sulfides are intrinsically fast catalysts, but they have few active sites and are prone to coking. In general, methanol TPSR is proposed as an accessible route to count sites on both supported oxides and sulfides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sulfide precipitation characteristics of Mn, Ni, Co, and Zn in the presence of contaminant metal ions

In this study, the effects of Al 3+ and Fe 2+ on the precipitation characteristics of four valuable metals, including Mn 2+ , Ni 2+ , Co 2+ , and Zn 2+ , were investigated by conducting solution chemistry calculations, sulfide precipitation tests, and mineralogy characterizations. It was found that the ability of the valuable metals to form sulfide precipitates followed an order of Zn 2+ > Ni 2+ > Co 2+ > Mn 2+ . The sulfide precipitate of Zn 2+ was the most stable and did not re-dissolve under the acidic condition (pH 4.00 ± 0.05). In addition, the sulfide precipitation characteristics of Zn 2+ was barely affected by the contaminant metal ions. However, in the presence of Al 3+ , the precipitation recoveries of Mn 2+ , Ni 2+ , and Co 2+ were noticeably reduced due to simultaneous hydrolysis and competitive adsorption. The precipitation recoveries of Ni 2+ and Co 2+ in solutions containing individual valuable metals also reduced when Fe 2+ was present, primarily due to competitive precipitation. However, the recovery of Mn 2+ was enhanced due to the formation of ferrous sulfide precipitate, providing abundant active adsorption sites for Mn species. Here, in the solution containing all the valuable metals, Fe 2+ promoted the recovery of the valuable metals due to the higher concentration of Na 2 S and the formation of ferrous sulfide precipitate.

58 GEOSCIENCES↗

Recent Progress on Dominant Sulfide‐Type Solid‐State Na Superionic Conductors for Solid‐State Sodium Batteries

Abstract Over the past decade, solid‐state batteries have garnered significant attentions due to their potentials to deliver high energy density and excellent safety. Considering the abundant sodium (Na) resources in contrast to lithium (Li), the development of sodium‐based batteries has become increasingly appealing. Sulfide‐based superionic conductors are widely considered as promising solid eletcrolytes (SEs) in solid‐state Na batteries due to the features of high ionic conductivity and cold‐press densification. In recent years, tremendous efforts have been made to investigate sulfide‐based Na‐ion conductors on their synthesis, compositions, conductivity, and the feasibility in batteries. However, there are still several challenges to overcome for their practical applications in high performance solid‐state Na batteries. This article provides a comprehensive update on the synthesis, structure, and properties of three dominant sulfide‐based Na‐ion conductors (Na 3 PS 4 , Na 3 SbS 4 , and Na 11 Sn 2 PS 12 ), and their families that have a variety of anion and cation doping. Additionally, the interface stability of these sulfide electrolytes toward the anode is reviewed, as well as the electrochemical performance of solid‐state Na batteries based on different types of cathode materials (metal sulfides, oxides, and organics). Finally, the perspective and outlook for the development and practical utilization of sulfide‐based SE in solid‐state batteries are discussed.

Guo, Xiaolin↗

Self‐Templated 3D Sulfide‐Based Solid Composite Electrolyte for Solid‐State Sodium Metal Batteries

Abstract Rechargeable solid‐state sodium metal batteries (SSMBs) experience growing attention owing to the increased energy density (vs Na‐ion batteries) and cost‐effective materials. Inorganic sulfide‐based Na‐ion conductors also possess significant potential as promising solid electrolytes (SEs) in SSMBs. Nevertheless, due to the highly reactive Na metal, poor interface compatibility is the biggest obstacle for inorganic sulfide solid electrolytes such as Na 3 SbS 4 to achieve high performance in SSMBs. To address such electrochemical instability at the interface, new design of sulfide SE nanostructures and interface engineering are highly essential. In this work, a facile and straightforward approach is reported to prepare 3D sulfide‐based solid composite electrolytes (SCEs), which utilize porous Na 3 SbS 4 (NSS) as a self‐templated framework and fill with a phase transition polymer. The 3D structured SCEs display obviously improved interface stability toward Na metal than pristine sulfide. The assembled SSMBs (with TiS 2 or FeS 2 as cathodes) deliver outstanding electrochemical cycling performance. Moreover, the cycling of high‐voltage oxide cathode Na 0.67 Ni 0.33 Mn 0.67 O 2 (NNMO) is also demonstrated in SSMBs using 3D sulfide‐based SCEs. This study presents a novel design on the self‐templated nanostructure of SCEs, paving the way for the advancement of high‐energy sodium metal batteries.

Guo, Xiaolin↗