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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Temperature-Dependent Reaction Pathways in FeS 2 : Reversibility and the Electrochemical Formation of Fe 3 S 4

The present study has used a variety of characterization techniques to determine the products and reaction pathways involved in the rechargeable Li–FeS 2 system. We revisit both the initial lithiation and subsequent cycling of FeS 2 employing an ionic liquid electrolyte to investigate the intermediate and final charge products formed under varying thermal conditions (room temperature to 100 °C). The detection of Li 2 S and hexagonal FeS as the intermediate phases in the initial lithiation and the electrochemical formation of greigite, Fe 3 S 4 , as a charge product in the rechargeable reaction differ significantly from previous reports. The conditions for Fe 3 S 4 formation are shown to be dependent on both the temperature (~60 °C) and the availability of sulfur to drive a FeS to Fe 3 S 4 transformation. Upon further cycling, Fe 3 S 4 transforms to a lower sulfur content iron sulfide phase, a process which coincides with the loss of sulfur based on the new reaction pathways established in this work. The connection between sulfur loss, capacity fade, and charge product composition highlights the critical need to retain sulfur in the active material upon cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A pseudo-two-dimensional (P2D) model for FeS 2 conversion cathode batteries

Conversion cathode materials are gaining interest for secondary batteries due to their high theoretical energy and power density. However, practical application as a secondary battery material is currently limited by practical issues such as poor cyclability. To better understand these materials, we have, for this study, developed a pseudo-two-dimensional model for conversion cathodes. We apply this model to FeS 2 – a material that undergoes intercalation followed by conversion during discharge. The model is derived from the half-cell Doyle–Fuller–Newman model with additional loss terms added to reflect the converted shell resistance as the reaction progresses. We also account for polydisperse active material particles by incorporating a variable active surface area and effective particle radius. Using the model, we show that the leading loss mechanisms for FeS 2 are associated with solid-state diffusion and electrical transport limitations through the converted shell material. The polydisperse simulations are also compared to a monodisperse system, and we show that polydispersity has very little effect on the intercalation behavior yet leads to capacity loss during the conversion reaction. Finally, we provide the code as an open-source Python Battery Mathematical Modeling (PyBaMM) model that can be used to identify performance limitations for other conversion cathode materials.

25 ENERGY STORAGE↗
DOE OSTI2022

Understanding the Electrochemical Performance of FeS 2 Conversion Cathodes

Conversion cathodes represent a viable route to improve rechargeable Li + battery energy densities, but their poor electrochemical stability and power density have impeded their practical implementation. Here, we explore the impact cell fabrication, electrolyte interaction, and current density have on the electrochemical performance of FeS 2 /Li cells by deconvoluting the contributions of the various conversion and intercalation reactions to the overall capacity. By varying the slurry composition and applied pressure, we determine that the capacity loss is primarily due to the large volume changes during (de)lithiation, leading to a degradation of the conductive matrix. Through the application of an external pressure, the loss is minimized by maintaining the conductive matrix. Further, we determine that polysulfide loss can be minimized by increasing the current density (>C/10), thus reducing the sulfur formation period. Analysis of the kinetics determines that the conversion reactions are rate-limiting, specifically the formation of metallic iron at rates above C/8. While focused on FeS 2 , our findings on the influence of pressure, electrolyte interaction, and kinetics are broadly applicable to other conversion cathode systems.

Pressure↗
DOE OSTI2024

Theoretical design and performance of three-dimensional, pillared FeS 2 cathodes

Three-dimensional (3D) electrode design can provide improved capacities and rate capabilities over conventional two-dimensional electrodes by enhancing electrical and ionic transport. Here, expanding upon our previous modeling efforts for conversion chemistry lithium-ion batteries, we develop a pseudo-four-dimensional (P4D) approach that is subsequently used to investigate the design of a pillared FeS 2 electrode. The model considers transport in three dimensions with an additional “fourth” dimension corresponding to the solid-state lithium transport within the active material particles. Additionally, we allow for expansion of the active material during the conversion reaction to understand how internal stresses impact the electrochemical performance of the cell. By optimizing the model with respect to areal capacity, we are able to predict areal capacities up to 16.8 mAh/cm 2 for an areal current density of 1.78 mA/cm 2 and a 103% improvement for the three-dimensional electrodes over planar electrodes of equal volume. Despite the promising results, our simulations suggest that 3D design may be difficult for conversion cathode materials due to the large internal stresses that arise during conversion. Nevertheless, the model is robust and adaptable to other materials that may be more suitable for 3D electrodes due to a lesser change in volume during discharge.

Conversion cathode materials↗
DOE OSTI2022

Promoting Reversibility of Multielectron Redox in Alkali-Rich Sulfide Cathodes through Cryomilling

We report conventional cathodes for Li-ion batteries (LIBs) are reaching their theoretical capacity limits. One way to meet the growing demands for high-capacity LIBs is by developing so-called Li-rich cathode materials that greatly benefit from additional capacities from anionic moieties in the structure. Li-rich materials are intrinsically subject to higher degrees of (de)intercalation, leaving the particles more prone to fractures and thus rapid capacity fade. Alkali-rich LiNaFeS 2 reversibly cycles with capacities exceeding 300 mAh g -1 , but its capacity fades faster than an isostructural material Li 2 FeS 2 . Using synchrotron-based transmission X-ray microscopy (TXM), we demonstrate that the capacity fade of LiNaFeS 2 stems from particle fractures in the first charge cycle. We improve the cycling performance of LiNaFeS 2 by means of cryomilling, which enhances capacity retention at cycle 50 by 76%. Through crystallographic and morphological characterization techniques, we confirm that cryomilling not only decreases particle and crystallite size while increasing microstrain but also prevents particles from fracturing. Cryomilling is a powerful tool to engineer nanoscale battery materials, and TXM allows the direct observation of morphological changes of the particles, which can be leveraged to develop next-generation cathode materials for LIBs.

25 ENERGY STORAGE↗
DOE OSTI2025

High-Energy Density Li-Ion Battery Cathode Using Only Industrial Elements

Li-ion batteries are crucial for the global energy transition to renewables; however, their scalability is limited by the supply of key elements used in commercial cathodes (e.g., Ni, Mn, Co, P). Therefore, there is an urgent need for next-generation cathodes composed of widely available and industrially scalable elements. Here, we introduce a Li-rich cathode based on the known material Li 2 FeS 2 , composed of low-cost elements (Al, Fe, S) that are globally mined and refined at an industrial scale. The substitution of redox-inactive Al 3+ for Fe 2+ achieves remarkably high degrees of anion redox, which, in turn, yields high gravimetric capacity (≈450 mAh·g –1 ) and energy density (≳1000 Wh·kg –1 ). We show that Al 3+ enables high degrees of delithiation by stabilizing the delithiated state, suppressing phase transformations that would otherwise prevent deep delithiation and extensive anion redox. This mechanistic insight offers new possibilities for developing scalable, next-generation Li-ion battery cathodes to meet pressing societal needs.

25 ENERGY STORAGE↗
DOE OSTI2022

Investigating Abiotic and Biotic Mechanisms of Pyrite Reduction

Pyrite (FeS 2 ) has a very low solubility and therefore has historically been considered a sink for iron (Fe) and sulfur (S) and unavailable to biology in the absence of oxygen and oxidative weathering. Anaerobic methanogens were recently shown to reduce FeS 2 and assimilate Fe and S reduction products to meet nutrient demands. However, the mechanism of FeS 2 mineral reduction and the forms of Fe and S assimilated by methanogens remained unclear. Thermodynamic calculations described herein indicate that H 2 at aqueous concentrations as low as 10 –10 M favors the reduction of FeS 2 , with sulfide (HS – ) and pyrrhotite (Fe 1–x S) as products; abiotic laboratory experiments confirmed the reduction of FeS 2 with dissolved H 2 concentrations greater than 1.98 × 10 –4 M H 2 . Growth studies of Methanosarcina barkeri provided with FeS 2 as the sole source of Fe and S resulted in H 2 production but at concentrations too low to drive abiotic FeS 2 reduction, based on abiotic laboratory experimental data. A strain of M. barkeri with deletions in all [NiFe]-hydrogenases maintained the ability to reduce FeS 2 during growth, providing further evidence that extracellular electron transport (EET) to FeS 2 does not involve H 2 or [NiFe]-hydrogenases. Physical contact between cells and FeS 2 was required for mineral reduction but was not required to obtain Fe and S from dissolution products. The addition of a synthetic electron shuttle, anthraquinone-2,6-disulfonate, allowed for biological reduction of FeS 2 when physical contact between cells and FeS 2 was prohibited, indicating that exogenous electron shuttles can mediate FeS 2 reduction. Here, transcriptomics experiments revealed upregulation of several cytoplasmic oxidoreductases during growth of M. barkeri on FeS 2 , which may indicate involvement in provisioning low potential electrons for EET to FeS 2 . Collectively, the data presented herein indicate that reduction of insoluble FeS 2 by M. barkeri occurred via electron transfer from the cell surface to the mineral surface resulting in the generation of soluble HS – and mineral-associated Fe 1–x S. Solubilized Fe(II), but not HS – , from mineral-associated Fe 1–x S reacts with aqueous HS – yielding aqueous iron sulfur clusters (FeS aq ) that likely serve as the Fe and S source for methanogen growth and activity. FeS aq nucleation and subsequent precipitation on the surface of cells may result in accelerated EET to FeS 2 , resulting in positive feedback between cell activity and FeS 2 reduction.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Reductive biomining of pyrite by methanogens

Pyrite (FeS 2 ) is the most abundant iron sulfide mineral in Earth’s crust. Until recently, FeS 2 has been considered a sink for iron (Fe) and sulfur (S) at low temperature in the absence of oxygen or oxidative weathering, making these elements unavailable to biology. However, anaerobic methanogens can transfer electrons extracellularly to reduce FeS 2 via direct contact with the mineral. Reduction of FeS 2 occurs through a multistep process that generates aqueous sulfide (HS – ) and FeS 2 -associated pyrrhotite (Fe 1-x S). Subsequent dissolution of Fe 1-x S provides Fe(II) (aq) , but not HS – , that rapidly complexes with HS – (aq) generated from FeS 2 reduction to form soluble iron sulfur clusters [nFeS (aq) ]. Cells assimilate nFeS (aq) to meet Fe/S nutritional demands by mobilizing and hyperaccumulating Fe and S from FeS 2 . As such, reductive dissolution of FeS 2 by methanogens has important implications for element cycling in anoxic habitats, both today and in the geologic past.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A shift between mineral and nonmineral sources of iron and sulfur causes proteome-wide changes in Methanosarcina barkeri

ABSTRACT Iron (Fe) and sulfur (S) are required elements for life, and changes in their availability can limit the ecological distribution and function of microorganisms. In anoxic environments, soluble Fe typically exists as ferrous iron [Fe(II)] and S as sulfide (HS − ). These species exhibit a strong affinity that ultimately drives the formation of sedimentary pyrite (FeS 2 ). Recently, paradigm-shifting studies indicate that Fe and S in FeS 2 can be made bioavailable by methanogens through a reductive dissolution process. However, the impact of the utilization of FeS 2 , as opposed to canonical Fe and S sources, on the phenotype of cells is not fully understood. Here, shotgun proteomics was utilized to measure changes in the phenotype of Methanosarcina barkeri MS grown with FeS 2 , Fe(II)/HS − , or Fe(II)/cysteine. Shotgun proteomics tracked 1,019 proteins overall, with 307 observed to change between growth conditions. Functional characterization and pathway analyses revealed these changes to be systemic and largely tangential to Fe/S metabolism. As a final step, the proteomics data were viewed with respect to previously collected transcriptomics data to deepen the analysis. Presented here is evidence that M. barkeri adopts distinct phenotypes to exploit specific sources of Fe and S in its environment. This is supported by observed protein abundance changes across broad categories of cellular biology. DNA adjacent metabolism, central carbon metabolism methanogenesis, metal trafficking, quorum sensing, and porphyrin biosynthesis pathways are all features in the phenotypic differentiation. Differences in trace metal availability attributed to complexation with HS − , either as a component of the growth medium [Fe(II)/HS − ] or generated through reduction of FeS 2 , were likely a major factor underpinning these phenotypic differences. IMPORTANCE The methanogenic archaeon Methanosarcina barkeri holds great potential for industrial bio-mining and energy generation technologies. Much of the biochemistry of this microbe is poorly understood, and its characterization will provide a glimpse into biological processes that evolved close to life’s origin. The discovery of its ability to extract iron and sulfur from bulk, solid-phase minerals shifted a longstanding paradigm that these elements were inaccessible to biological systems. The full elucidation of this process has the potential to help scientists and engineers extract valuable metals from low-grade ore and mine waste generating energy in the form of methane while doing so.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Impact of mineral and non-mineral sources of iron and sulfur on the metalloproteome of Methanosarcina barkeri

Methanogens often inhabit sulfidic environments that favor the precipitation of transition metals such as iron (Fe) as metal sulfides, including mackinawite (FeS) and pyrite (FeS 2 ). These metal sulfides have historically been considered biologically unavailable. Nonetheless, methanogens are commonly cultivated with sulfide (HS - ) as a sulfur source, a condition that would be expected to favor metal precipitation and thus limit metal availability. Recent studies have shown that methanogens can access Fe and sulfur (S) from FeS and FeS 2 to sustain growth. As such, medium supplied with FeS 2 should lead to higher availability of transition metals when compared to medium supplied with HS - . Here, we examined how transition metal availability under sulfidic (i.e., cells provided with HS - as sole S source) versus non-sulfidic (cells provided with FeS 2 as sole S source) conditions impact the metalloproteome of Methanosarcina barkeri Fusaro. To achieve this, we employed size exclusion chromatography coupled with inductively coupled plasma mass spectrometry and shotgun proteomics. Significant changes were observed in the composition and abundance of iron, cobalt, nickel, zinc, and molybdenum proteins. Among the differences were alterations in the stoichiometry and abundance of multisubunit protein complexes involved in methanogenesis and electron transport chains. Furthermore, our data suggest that M. barkeri utilizes the minimal iron-sulfur cluster complex and canonical cysteine biosynthesis proteins when grown on FeS 2 but uses the canonical Suf pathway in conjunction with the tRNA-Sep cysteine pathway for iron-sulfur cluster and cysteine biosynthesis under sulfidic growth conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

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↗
DOE OSTI2025

Photocatalytic Activity and Stability of Carbon Nitride‐Pyrite Composites

Abstract In photocatalysis, the photoabsorber plays a crucial role in the reaction. The most important parameters are stability, cost and optical band gap. In this work, a prominent class of absorbers, namely carbon nitrides (CN), has been investigated. In the literature, CN is most often described as stable, although photodegradation has been observed. In order to retain the beneficial properties of CN while improving stability, a crystalline phase poly(triazine imide) (PTI) of carbon nitride was investigated and compared to polymeric CN in photocatalytic hydrogen generation experiments. In order to improve the charge separation for the photoinduced hydrogen evolution reaction, pyrite (FeS 2 ) was used as a surface co‐catalyst with a loading of 1, 5 and 10 wt %. At the same time, any photodegradation products in solution were investigated by ion chromatography. Interestingly, PTI shows hardly any photocorrosion compared to defective carbon nitride, indicating its higher photostability in hydrogen evolution experiments. However, FeS 2 produces ammonium as a degradation product when synthesised from nitrogen‐containing precursors. When made from nitrogen‐free precursors, FeS 2 together with photostable PTI releases little ammonia, making it a photostable, earth‐abundant composite for photocatalytic hydrogen generation.

Kaulbersch, Julian [University of Bayreuth 95440 B↗
DOE OSTI2023

Microwave-assisted synthesis of iron sulfide motifs for electrochemical applications

Abstract The syntheses of FeS 2 and Fe 3 S 4 nanomaterials were optimized using a novel facile, surfactant-free, and microwave-assisted, one-pot synthesis method, run under ambient and reasonably mild reaction conditions. Synthetic parameters, such as metal precursor salt identity, reaction time, reaction temperature, metal:sulfur molar ratios, and solvent combinations, were all systematically investigated and optimized. A series of FeS 2 (pyrite) samples was initially fabricated using thioacetamide (TAA) as the sulfur precursor to generate a distinctive, uniform octahedra-based morphology. Switching the sulfur precursor from TAA to L-cysteine resulted in a corresponding transformation in not only chemical composition from FeS 2 to an iron thiospinel structure, Fe 3 S 4 (otherwise known as greigite), but also an associated morphological evolution from octahedra to nanosheet aggregates. The study of these materials has enabled crucial insights into the formation mechanisms of these materials under a relatively non-conventional microwave-assisted setting. Furthermore, in separate experiments, multi-walled carbon nanotubes (MWNTs) and graphene were added in with underlying metal sulfide species to create conductive Fe–S/MWNT composites and Fe–S/graphene composites, respectively. The method of addition of either MWNTs or graphene was also explored, wherein an ‘ ex-situ ’ synthetic procedure was found to be the least disruptive means of attachment and immobilization onto iron sulfide co-reagents as a means of preserving the latter’s inherent composition and morphology. The redox acidity for the parent material and associated composites demonstrates the utility of our as-developed synthetic methods for creating motifs relevant for electrochemical applications, such as energy storage.

25 ENERGY STORAGE↗
DOE OSTI2021

Conduction via surface states in antiferromagnetic Mott-insulating Ni S 2 single crystals

Pyrite structure transition-metal disulfides exhibit diverse ground states vs d-band filling, spanning diamagnetic semiconducting, ferromagnetic metallic, antiferromagnetic Mott insulating, and superconducting in FeS 2 , CoS 2 , NiS 2 , and CuS 2 . NiS is particularly interesting and poorly understood as its Mott insulating behavior is accompanied by complex antiferromagnetic ordering below ~38 K and perplexing weak ferromagnetism below ~30 K. Temperature-, pressure-, and composition-dependent insulator-metal transitions also occur, particularly in bandwidth-controlled NiS 2–x Se x , hole-doped Ni 1–x Co x S 2 , etc. Here, we use high-quality chemical-vapor-transport-grown NiS 2 single crystals characterized by x-ray diffraction, energy-dispersive x-ray spectroscopy, magnetometry, and extensive transport and magnetotransport measurements, to generate new insight into this system. In particular, resistivity, magnetoresistance, and Hall effect analyses vs temperature, thickness, and surface preparation, provide unequivocal evidence of surface conduction, where the more conductive surface shunts essentially all current at low temperatures. The surface transport changes from two dimensional and insulating to three dimensional and metallic as the surface preparation is varied (also displaying intriguing sensitivity to magnetic ordering), significantly clarifying literature ambiguities with respect to the electronic ground state. These results have immediate implications. First, the temperature-, pressure-, and composition-dependent insulator-metal transitions deduced in the extensive prior work on NiS 2-x Se x , Ni 1–x Co x S 2 , etc., must clearly be reexamined in light of rife metallic surface conduction, not previously taken into account. Second, NiS 2 now joins FeS 2 and CoS 2 as systems in which bulk and surface electronic behaviors are strikingly different, suggesting that metallic surface states could be a universal feature of pyrite structure transition-metal disulfides.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Molecular Insights into Geochemical Reactions of Iron-Bearing Minerals: Implications for Hydrogen Geo-Storage

Here, this study investigates the reaction of hydrogen (H 2 ) with pyrite (FeS 2 ), focusing on how temperature and the presence of water influence the reaction pathways and kinetics. Utilizing computational molecular simulations and kinetic analyses, we explore the impact of these factors on the formation of hydrogen sulfide (H 2 S) and related species. First, grand canonical Monte Carlo/molecular dynamics (GCMC/MD) simulations reveal that physical H 2 adsorption occurs in distinct layers on the pyrite surface. In addition, increased temperatures reduce the absolute adsorption capacities. Reactive MD simulations demonstrate that H 2 interacts differently with pyrite under varying conditions. At 298 K, H 2 reacts with pyrite to form HS – , leading to the formation of HS – through covalent bonding with sulfur of pyrite. However, no H 2 S is produced at this temperature, suggesting that a kinetic barrier (i.e., activation energy) may prevent this reaction. At higher temperatures, H 2 S production significantly increases. The presence of water introduces additional complexity to the reaction mechanism. Unlike dry conditions, water enhances H 2 S generation, even at low temperatures. Water also facilitates the formation of additional products, such as SOH, indicating a more intricate chemical environment on the pyrite surface. Our findings identify the association of HS – ions to form H 2 S as the rate-limiting step, with temperature influencing this process. This finding suggests that while the presence of water can create a more dynamic reaction environment, the overall mechanisms leading to H 2 S formation remain consistent. These outcomes suggest the need for developing targeted strategies to manage and control H 2 S emissions within the context of underground hydrogen storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Development of molecular cluster models to probe pyrite surface reactivity

Abstract The recent discovery that anaerobic methanogens can reductively dissolve pyrite and utilize dissolution products as a source of iron and sulfur to meet their biosynthetic demands for these elements prompted the development of atomic‐scale nanoparticle models, as maquettes of reactive surface sites, for describing the fundamental redox steps that take place at the mineral surface during reduction. The given report describes our computational approach for modeling n (FeS 2 ) nanoparticles originated from mineral bulk structure. These maquettes contain a comprehensive set of coordinatively unsaturated Fe (II) sites that are connected via a range of persulfide (S 2 2− ) ligation. In addition to the specific maquettes with n = 8, 18, and 32 FeS 2 units, we established guidelines for obtaining low‐energy structures by considering the pattern of ionic, covalent, and magnetic interactions among the metal and ligand sites. The developed models serve as computational nano‐reactors that can be used to describe the reductive dissolution mechanism of pyrite to better understand the reactive sites on the mineral, where microbial extracellular electron‐transfer reactions can occur.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Phase-field modeling of solid-state metathesis reactions with the charge neutrality constraint

In this work, we present a phase-field model that captures the evolution of ionic concentrations and phase fractions during solid-state metathesis (SSM) reactions where diffusion limits the rate of transformation. The evolution of the mole fraction of each ion is obtained via governing equations that describe the reduction of a free energy, which includes an energy landscape with local minima located at compositions corresponding to stable products. We utilized two Lagrange multipliers to impose constraints of electroneutrality as well as on the sum of mole fractions, which were then eliminated to derive set of two partial differential equations that describe the dynamics of the mole fraction evolution. From these governing equations, the expressions for effective mobilities for the cations and the anions were obtained. We first study the effect of mobilities of ions on the reaction kinetics, using a simple model considering the ions with an identical absolute value of charge numbers. The simulation results show that the overall characteristic mobility, defined as the sum of the two effective ionic mobilities, provides an excellent measure of the rate at which reaction progresses and that the ratio of the effective mobilities of the anions and the cations signifies the manner by which the reaction progresses. We then generalize the model to consider ions with different charge numbers and tuned the mobility of ions based on their diffusion coefficients reported in the literature and experimental data from a thin-film experiment for the synthesis of FeS 2 to demonstrate the capability of the model to predict the phase evolution during SSM reactions. In particular, the simulation predicts nonplanar phase evolution, which is recently observed in thin-film reactions for the synthesis of FeS 2 via transmission electron microscopy. The approach can serve as a basis for models for phase transformations in other multiphase ionic mixtures, such as in all-solid-state batteries and in ionic liquids.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Proteomic Analysis of Methanococcus voltae Grown in the Presence of Mineral and Nonmineral Sources of Iron and Sulfur

Iron sulfur (Fe-S) proteins are essential and ubiquitous across all domains of life, yet the mechanisms underpinning assimilation of iron (Fe) and sulfur (S) and biogenesis of Fe-S clusters are poorly understood. This is particularly true for anaerobic methanogenic archaea, which are known to employ more Fe-S proteins than other prokaryotes. Here, we utilized a deep proteomics analysis of Methanococcus voltae A3 cultured in the presence of either synthetic pyrite (FeS 2 ) or aqueous forms of ferrous iron and sulfide to elucidate physiological responses to growth on mineral or nonmineral sources of Fe and S. The liquid chromatography-mass spectrometry (LCMS) shotgun proteomics analysis included 77% of the predicted proteome. Through a comparative analysis of intra- and extracellular proteomes, candidate proteins associated with FeS 2 reductive dissolution, Fe and S acquisition, and the subsequent transport, trafficking, and storage of Fe and S were identified. The proteomic response shows a large and balanced change, suggesting that M. voltae makes physiological adjustments involving a range of biochemical processes based on the available nutrient source. Among the proteins differentially regulated were members of core methanogenesis, oxidoreductases, membrane proteins putatively involved in transport, Fe-S binding ferredoxin and radical S-adenosylmethionine proteins, ribosomal proteins, and intracellular proteins involved in Fe-S cluster assembly and storage. This work improves our understanding of ancient biogeochemical processes and can support efforts in biomining of minerals. Clusters of iron and sulfur are key components of the active sites of enzymes that facilitate microbial conversion of light or electrical energy into chemical bonds. The proteins responsible for transporting iron and sulfur into cells and assembling these elements into metal clusters are not well understood. Using a microorganism that has an unusually high demand for iron and sulfur, we conducted a global investigation of cellular proteins and how they change based on the mineral forms of iron and sulfur. Understanding this process will answer questions about life on early earth and has application in biomining and sustainable sources of energy.

59 BASIC BIOLOGICAL SCIENCES↗