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At least 19 records

Effect of Block Length on the Properties of Multiblock Polysulfone-Poly(diallylpiperidinium hydroxide) Anion Exchange Membranes

Research in anion exchange membranes (AEM)s has continued with the development of materials bearing base stable cations. Designing AEMs that microphase separate into hydroxide conductive, hydrophilic domains within a hydrophobic and mechanically robust matrix has been shown to be successful for improving AEM performance. A series of multiblock polysulfone-poly(diallylpiperidinium hydroxide) copolymers (PSf-PDApipOH) of similar hydrophobic/hydrophilic composition was prepared in which the molecular weight of the hydroxide conducting PDApipOH segments was varied. The variable hydrophilic segment molecular weight was designed to assess the impact on microphase separation, hydroxide conductivity, and water management. The multiblock copolymers investigated were prepared by condensation polymerization of preformed4-fluorophenyl sulfone terminated poly(diallylpiperidinium hexafluorophosphate) (PDApipPF6) oligomers with polysulfone monomers. The structure-property relationship between the molecular weight of the conductive PDApipOH segments and AEM performance was demonstrated by evaluation of the microphase separation, water uptake, and hydroxide conductivity. Further, membranes fabricated from the polysulfone-poly(diallylpiperidinium hexafluorophosphate) (PSf-PDApipPF6) multiblock copolymers were shown to form well-connected conductive domains by SAXS and atomic force microscopy experiments. The PSf-PDApipOH membranes were highly conductive with the maximum hydroxide conductivity reaching 62.9 mS∙cm -1 at 60°C and 95% relative humidity. Furthermore, it was demonstrated that the conductivity increased with increasing PDApipOH segment molecular weight.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics of resonant low-energy electron attachment to ethanol-producing hydroxide anions

Here, the dynamics of dissociative electron attachment to ethanol is experimentally investigated at the Feshbach resonance formed with incident electron energies near 9.5 eV. Highly differential laboratory-frame momentum distributions of OH – fragments are measured for a series of energies spanning the resonance width, using the velocity-map-imaging technique. The OH – kinetic-energy distribution indicates that the C-O breaking dissociation process could either be a three-body dissociation or a two-body dissociation with significant rovibrational excited fragments. The small, but significant, anisotropy in the OH – angular distribution provides signatures of the molecular symmetry of the associated resonant state under the axial recoil approximation, which assumes the dissociation is much faster than any rotation of the dissociation axis. Within these assumptions, the 9.5-eV Feshbach resonance can be assigned to the electronic transition from the ($10a'$) orbital with its ground-state C s symmetry to the empty ($4a''$) level, involving the simultaneous electron attachment. This dynamics could be a model for C-O dissociation in larger alcohols and ethers.

74 ATOMIC AND MOLECULAR PHYSICS↗

Phosphate anion-quaternary ammonium ion pair coordinated polymer membranes

Ion exchange membranes materials according to the present disclosure exhibit improved conductivity at low and intermediate relative humidity without sacrificing mechanical strength. Polymers are provided that include a backbone with one or more aryl groups, a halocarbyl group, and a halocarbyl side chain attached to the backbone, wherein the halocarbyl side chain includes a halide separated from the backbone by a hydrocarbyl chain, a hydrocarbyl ring, or combinations thereof. The halide is substituted with a tertiary amine and halide anions are then exchanged with hydroxide anions. The polymers are then contacted with phosphoric acid, which is deprotonated by the hydroxide ions, forming anions which enhance interactions with adjacent quaternary ammonium groups and induce excess phosphoric acid molecules to cluster around those quaternary ammonium groups. The membranes exhibit negligible dopant leaching even at high relative humidity.

Bae, Chulsung↗

Layered hydroxides as anion insertion materials

Further described herein are extensions to the basic concept of LHs as electrode materials, include both new materials for use with LHs and higher order poly-layer hydroxides (PLHs) as well as methods for synthesizing improved LH material such as with conductive supports or through the use of cross-linking. Finally, also described herein are embodiments enabling the use of LHs as flow electrodes as well as the use of 2-d LH materials for surface redox reactions.

Young, Matthias J.↗

Investigating Morphology and Diffusion in Simulations of Precise Anion-Conducting Polymers

Using atomistic molecular dynamics simulations, we investigate the morphology and transport properties of a new class of polymers which are functionalized with quaternary ammonium groups for use as anion exchange membranes. The polymers are precision polyolefins with either a trimethylammonium (p5CNMe3) or a dimethyl-hexyl ammonium (p5CNMe2Hx) pendant group at every fifth carbon along a polyethylene backbone. Simulations are performed at hydration levels of 5, 10, 15, and 20 water molecules per ammonium group. The hydrated polymers form nanoscale, percolated hydrophilic domains (water channels) in the hydrophobic polymer matrix that become wider with increasing water content. Water and hydroxide anion diffusion coefficients also increase with increasing water content. The morphology of the water domains is similar in both polymers, while the diffusion coefficients are somewhat lower in p5CNMe2Hx at fixed water content. Furthermore, the diffusion coefficients in both polymers fall on the same curve as a function of the fractal dimension of the percolated water channels, which appears to be a useful scalar measure of the effects of the nanoscale morphology on water and hydroxide anion transport.

Anion exchange membrane↗

Hydrated Anions: From Clusters to Bulk Solution with Quasi-Chemical Theory

The interactions of hydrated ions with molecular and macromolecular solution and interface partners are strong on a chemical energy scale. Here we recount the foremost ab initio theory for the evaluation of the hydration free energies of ions, namely, quasi-chemical theory (QCT). We focus on anions, particularly halides but also the hydroxide anion, because they have been outstanding challenges for all theories. For example, this work supports understanding the high selectivity for F – over Cl – in fluoride-selective ion channels despite the identical charge and the size similarity of these ions. QCT is built by the identification of inner-shell clusters, separate treatment of those clusters, and then the integration of those results into the broader-scale solution environment. Recent work has focused on a close comparison with mass-spectrometric measurements of ion-hydration equilibria. We delineate how ab initio molecular dynamics (AIMD) calculations on ion-hydration clusters, elementary statistical thermodynamics, and electronic structure calculations on cluster structures sampled from the AIMD calculations obtain just the free energies extracted from the cluster experiments. That theory–experiment comparison has not been attempted before the work discussed here, but the agreement is excellent with moderate computational effort. This agreement reinforces both theory and experiment and provides a numerically accurate inner-shell contribution to QCT. The inner-shell complexes involving heavier halides display strikingly asymmetric hydration clusters. Asymmetric hydration structures can be problematic for the evaluation of the QCT outer-shell contribution with the polarizable continuum model (PCM). Nevertheless, QCT provides a favorable setting for the exploitation of PCM when the inner-shell material shields the ion from the outer solution environment. For the more asymmetrically hydrated, and thus less effectively shielded, heavier halide ions clustered with waters, the PCM is less satisfactory. We therefore investigate an inverse procedure in which the inner-shell structures are sampled from readily available AIMD calculations on the bulk solutions. This inverse procedure is a remarkable improvement; our final results are in close agreement with a standard tabulation of hydration free energies, and the final composite results are independent of the coordination number on the chemical energy scale of relevance, as they should be. Finally, a comparison of anion hydration structure in clusters and bulk solutions from AIMD simulations emphasize some differences: the asymmetries of bulk solution inner-shell structures are moderated compared with clusters but are still present, and inner hydration shells fill to slightly higher average coordination numbers in bulk solution than in clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stability Analysis of Substituted Cobaltocenium [Bis(cyclopentadienyl)cobalt(III)] Employing Chemistry-Informed Neural Networks

Cobaltocenium derivatives are promising components of the anion exchange membranes due to their excellent thermal and alkaline stability under the operating conditions of a fuel cell. Here we present an efficient modeling approach of assessing the chemical stability of substituted cobaltocenium CoCp 2 + based on the computed electronic structure enhanced by machine learning techniques. Within the aqueous environment, the positive charge of the metal cation is balanced by the hydroxide anion through formation of the CoCp 2 + OH¯ complexes, whose dissociation is studied within the implicit solvent employing density functional theory. The data set of about 118 species based on 42 substituent groups characterized by a range of electron- donating (ED) and electron-withdrawing (EW) properties is constructed and analyzed. Given 12 carefully chosen chemistry-informed descriptors of the complexes and relevant fragments, the stability of the complexes is found to strongly correlate with the energies of the highest occupied and lowest unoccupied molecular orbitals, modulated by a switching function of the Hirshfeld charge. The latter is used as a measure of the electron withdrawing-donating character of the substituents. Based on this observation from the conventional regression analysis, two fully connected, feed-forward neural network (FNN) models with different unit structures, called the chemistry-informed (CINN) and the quadratic (QNN) neural networks, are developed. Both models predict the bond dissociation energies of the cobaltocenium complexes with mean relative errors less than 5.40% and average absolute errors less than 0.94 kcal/mol. The results show the potential of QNN to efficiently capture more complex relationships. Here, the concept of incorporating the domain (chemical) knowledge/insight into the neural network structure paves the way to applications of machine learning techniques with small data sets, ultimately leading to better predictive models compared to the conventional regression analysis.

36 MATERIALS SCIENCE↗

Identification of a Na + -Binding Site near the Oxygen-Evolving Complex of Spinach Photosystem II

The oxygen-evolving complex (OEC) of photosystem II (PSII) is an oxomanganese cluster composed of four redox-active Mn ions, and one redox-inactive Ca 2+ ion, with two nearby bound Cl – ions. Sodium is a common counter-ion of both chloride and hydroxide anions, and a sodium-specific binding site has not been identified near the OEC. Furthermore, we find that the oxygen-evolution activity of spinach PSII increases with [Na + ], particularly at high pH. A Na + -specific binding site next to the OEC, upon deprotonation of the D1-H337 amino-acid residue, is suggested by the analysis of two recently published PSII cryo-EM maps in combination with quantum mechanical calculations and molecular dynamics simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Dicationic fac -Re(bpy)(CO) 3 Cl for CO 2 Electroreduction at a Reduced Overpotential

Here, a dicationic Re bipyridine-type complex, fac-Re(6,6'-(2-((trimethylammonio)-methyl)phenyl)-2,2'-bipyridine)(CO) 3 Cl hexafluorophosphate (1 2+ ), has been synthesized and its electrochemical behavior under Ar and CO 2 has been investigated. The presence of pendent tetra-alkylammonium cations induces an anodic shift in the electrocatalytic potential for CO 2 reduction relative to structurally similar model complexes. The electrochemical mechanisms in anhydrous CH 3 CN and in the presence of weak acids (water or trifluoroethanol) have been analyzed using cyclic voltammetry assisted by infrared spectroelectrochemistry and theoretical calculations. The dication enables catalysis at a diminished potential through coulombic stabilization of the doubly reduced pentacoordinate species, its CO 2 adduct, the hydroxide anion, and the conjugate base formed during acid-assisted C-OH bond cleavage of the metallocarboxylic acid to the metallocarbonyl and H 2 O. The major reduction product is CO, but in the presence of trifluoroethanol, formate is also produced with 14% Faradaic efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling Strong Light-Matter Coupling in Correlated Systems: State-Averaged Cavity Quantum Electrodynamics Complete Active Space Self-Consistent Field Theory

The description of strongly correlated systems interacting with quantized cavity modes poses significant theoretical challenges due to the combinatorial scaling of electronic and photonic degrees of freedom. Recent advances addressing this complexity include cavity quantum electrodynamics (QED) generalizations of complete active space configuration interaction and density matrix renormalization group methods. In this work, we introduce a QED extension of state-averaged complete active space self-consistent field theory, which incorporates cavity-induced correlations through a second-order orbital optimization framework with robust convergence properties. The method is implemented using both photon number state and coherent state representations, with the latter showing robust origin invariance in the energies regardless of the completeness of the photonic Fock space. The implementation enables symmetry-free orbital relaxations to account for photon-mediated symmetry breaking in polaritonic systems. Numerical validation on lithium hydride, hydroxide anion, and magnesium hydride cation demonstrates that this method achieves significantly improved accuracy in modeling ground-state and polariton potential energy surfaces compared to QED-CASCI in a fixed orbital basis. In these studies, we reach sub-kcal/mol accuracy in potential energy surface in much smaller active spaces than are required for QED-CASCI. This advancement provides a more robust approach for studying cavity-altered chemical landscapes for ground and exited strongly coupled systems.

CASSCF↗

Biomimetic Fe–Cu Porphyrrole Aerogel Electrocatalyst for Oxygen Reduction Reaction

The development of bioinspired catalysts for oxygen reduction reaction is one of the most prominent pathways in the search for active materials to replace Pt-based catalysts in fuel cells. Herein, we report innovative bioinspired catalysts using a directed synthetic pathway to create adjacent Cu and Fe sites. This catalyst is composed of a covalent 3D framework in an aerogel form. Aerogels are high surface area and porous hierarchical structures that can allow the formation of ultrahigh active site density and optimized mass transport of reactants and products to and from the catalytic sites. The aerogel-based catalyst exhibits high performance in a half-cell in 0.1 M KOH, with an onset potential of 0.94 V vs RHE and half-wave potential of E 1/2 = 0.80 V vs RHE, high selectivity toward the four-electron reduction of oxygen to hydroxide anions, and high durability. These results are well-translated to the anion exchange membrane fuel cell (AEMFC), reaching an open circuit potential of 0.97 V and iR-corrected peak power density of 0.51 W cm –2 . Based on density functional theory calculations, the improved activity relative to the Fe-porphyrin and Cu-corrole is ascribed to the effect of the extended carbon network and the proximity of the metal sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Energy- and carbon-efficient CO 2 /CO electrolysis to multicarbon products via asymmetric ion migration–adsorption

Carbon dioxide/monoxide (CO 2 /CO) electrolysis provides a means to convert emissions into multicarbon products. However, impractical energy and carbon efficiencies limit current systems. Here we show that these inefficiencies originate from uncontrolled gas/ion distributions in the local reaction environment. Understanding of the flows of cations and anions motivated us to seek a route to block cation migration to the catalyst surface-a strategy we instantiate using a covalent organic framework (COF) in bulk heterojunction with a catalyst. The pi-conjugated hydrophobic COFs constrain cation (potassium) diffusion via cation-pi interactions, while promoting anion (hydroxide) and gaseous feedstock adsorption on the catalyst surface. So as a result, a COF-mediated catalyst enables electrosynthesis of multicarbon products from CO for 200 h at a single-pass carbon efficiency of 95%, an energy efficiency of 40% and a current density of 240 mA cm -2 .

42 ENGINEERING↗

Synthesis of 2D layered transition metal (Ni, Co) hydroxides via edge-on condensation

Abstract Layered transition metal hydroxides (LTMHs) with transition metal centers sandwiched between layers of coordinating hydroxide anions have attracted considerable interest for their potential in developing clean energy sources and storage technologies. However, two-dimensional (2D) LTMHs remain largely understudied in terms of physical properties and applications in electronic devices. Here, for the first time we report > 20 μm α-Ni(OH) 2 2D crystals, synthesized from hydrothermal reaction. And an edge-on condensation mechanism assisted with the crystal field geometry is proposed to understand the 2D intra-planar growth of the crystals, which is also testified through series of systematic comparative studies. We also report the successful synthesis of 2D Co(OH) 2 crystals (> 40 μm) with more irregular shape due to the slightly distorted octahedral geometry of the crystal field. Moreover, the detailed structural characterization of synthesized α-Ni(OH) 2 are performed. The optical band gap energy is extrapolated as 2.54 eV from optical absorption measurements and the electronic bandgap is measured as 2.52 eV from reflected electrons energy loss spectroscopy (REELS). We further demonstrate its potential as a wide bandgap (WBG) semiconductor for high voltage operation in 2D electronics with a high breakdown strength, 4.77 MV/cm with 4.9 nm thickness. The successful realization of the 2D LTMHs opens the door for future exploration of more fundamental physical properties and device applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct observation of the local microenvironment in inhomogeneous CO 2 reduction gas diffusion electrodes via versatile pOH imaging

In this study, we report how the micrometer-scale morphology of a carbon dioxide reduction (CO 2 R) gas diffusion electrode (GDE) affects the mass transport properties and with it, the local CO 2 R performance. We developed a technique to probe the microenvironment in a CO 2 R GDE via local pOH imaging with time- and three-dimensional spatial, micrometer-scale resolution. The local activity of hydroxide anions (OH - ), represented by the pOH value, around a GDE in contact with an aqueous electrolyte is a crucial parameter that governs the catalytic activity and CO 2 R selectivity. Here, we use fluorescence confocal laser scanning microscopy (CLSM) to create maps of the local pOH around a copper GDE by combining two ratiometric fluorescent dyes, one of which is demonstrated as a pOH sensor for the first time in this work. We observe that the local pOH decreases when current is applied due to the creation of OH - as a byproduct of CO 2 R. Interestingly, the pOH is lower inside microtrenches compared to the electrode surface and decreases further as trenches become more narrow due to enhanced trapping of OH - . We support our experimental results with multiphysics simulations that correlate exceptionally well with measurements. These simulations additionally suggest that the decreased pOH inside microcavities in the surface of a CO 2 R GDE leads to locally enhanced selectivity towards multicarbon (C 2+ ) products. This study suggests that narrow microstructures on the length scale of 5 μm in a GDE surface serve as local CO 2 R hotspots, and thus highlights the importance of a GDE's micromorphology on the CO 2 R performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Processes Breaking Strict Phase Electroneutrality in Microemulsions

Phase electroneutrality is a near-omnipresent assumption in electrochemical reactions. Even media such as biphasic oil-water interfaces and kinetically stable emulsions follow this “rule.” This implies all electron transfer reactions must be accompanied by ion transfer to maintain charge balance within a phase. However, due to the small domain size, electroneutrality is known to break down in the electric double layer adjacent to the electrode. Therefore, the appropriateness of the electroneutrality approximation for media with nanoscale domains, such as microemulsions, is questionable. Here, in this work, we show definitively, for the first time, that phase electroneutrality can be violated during an electron transfer reaction in microemulsions. Cyclic voltammograms show that electrochemical oxidation of rubrene is possible in microemulsions when sodium hydroxide is the only supporting electrolyte. Rubrene is a hydrophobic redox compound that is insoluble in water in neutral and radical cation forms, and hydroxide anions are too hydrophilic to transfer to the oil (toluene) phase. Contrary to observations made in emulsion systems, rubrene oxidation in microemulsions seemingly occurs by a mechanism where coupled ion transfer required for rigorous phase electroneutrality is negated. Our results demonstrate that electron transfer reactions within nanometer-sized domains are not subject to restrictions that govern systems with larger domains.

Barth, Brian A. [Univ. of Tennessee, Knoxville, TN↗

Functional Ion Pair Receptors Targeting Cesium, Lithium, Sulfate, and Uranyl (Final Technical Report)

The major goal of this project was the synthesis and study of receptors for key ions of interest to the DOE mission, namely cesium, lithium, sulfate, hydroxide, carbon dioxide/bicarbonate, and early actinides. The work, fundamental in nature, had as its objective achieving an increased understanding of how changes in receptor design could be used to optimize binding energies, ion specificity, complex structure, extraction efficiency, and substrate release. Within this broad paradigm, particular emphasis was placed on systems that could be used to sense the cesium cation in mixed aqueous media and act as extractants for the lithium cation and, separately, the carbon dioxide/bicarbonate and hydroxide anions in the form of ion pairs likely to be encountered under conditions of putative use in the field. The development of new nitrogen-rich ligands that act as receptors for early, high-valent actinide cations was also a major point of emphasis. The first in-plane actinide complexes were synthesized using a hexa-aza porphyrin analogue. The complexes exhibited an increase in the ligand–metal bonding covalency on passing from thorium(IV) to uranium(IV) to neptunium(IV) and illustrates how the use of appropriate porphyrinoid-like ligands could be used to modulate the covalency interactions between an f-element metal center and a ligand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iron Mineralogy and Aqueous Alteration on Mars from the MER Moessbauer Spectrometers

The twin Mars Exploration Rovers Spirit (Gusev crater) and Opportunity (Meridiani Planum) used MIMOS II Moessbauer spectrometers to analyze martian surface materials in the first application of extraterrestrial Moessbauer spectroscopy. The instruments acquired spectra that identified the speciation of Fe according to oxidation state, coordination state, and mineralogical composition and provided quantitative information about the distribution of Fe among oxidation states, coordination states, and Fe-bearing phases. A total of 12 unique Fe-bearing phases were identified: Fe(2+) in olivine, pyroxene, and ilmenite; Fe(2+) and Fe(3+) in magnetite and chromite; Fe(3+) in nanophase ferric oxide (npOx), hematite, goethite, jarosite, an unassigned Fe3+ sulfate, and an unassigned Fe(3+) phase associated with jarosite; and Fe(0) in kamacite. Weakly altered basalts at Gusev crater (SO3 = 2.5 +/- 1.4 wt.% and Fe(3+)/Fe(sub T) = 0.24 +/- 0.11) are widespread on the Gusev plains and occur in less abundance on West Spur and Husband Hill in the Columbia Hills. Altered low-S rocks (SO3 = 5.2 +/- 2.0 wt.% and Fe(3+)/Fe(sub T) = 0.63 +/- 0.18) are the most common type of rock in the Columbia Hills. Ilm-bearing, weakly altered basalts were detected only in the Columbia Hills, as was the only occurrence of chromite in an altered low-S rock named Assemblee. Altered high-S rocks (SO3 > 14.2 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05) are the outcrop rocks of the ubiquitous Burns formation at Meridiani Planum. Two Fe(0)-bearing rocks at Meridiani Planum (Barberton and Heat Shield Rock) are meteorites. Laguna Class soil is weakly altered (SO3 = 6 +/- 2 wt.% and Fe(3+)/Fe(sub T) = 0.29 +/- 0.08) and widely distributed at both Gusev crater and Meridiani Planum, implying efficient global mixing processes or a global distribution of precursor rocks with comparable Fe mineralogical compositions. Paso Robles Class soil is heavily altered (SO3 approx. 31 wt.% and Fe(3+)/Fe(sub T) = 0.83 +/- 0.05), is relatively uncommon, and occurs as subsurface deposits in the Columbia Hills. Berry Class soil is also heavily altered (SO3 = 5 +/- 1 wt.% and Fe(3+)/Fe(sub T) = 0.60 +/- 0.13) and occurs at Meridiani Planum as lag deposits, at the crests of aeolian bedforms, and as isolated pockets on outcrop surfaces. Magnetite is identified as the strongly magnetic component in martian soil. Jarosite (in the Burns outcrop at Meridiani Planum) and goethite (in Clovis Class rocks at Gusev crater) are mineralogical markers for aqueous processes because they contain the hydroxide anion (OH(-)) as an essential part of their structure. Each yields approx.10 wt.% H2O upon dehydroxylation. The presence of Fe sulfates on opposite sides of Mars is evidence that aqueous processes under acid sulfate conditions are or were common. Except for Independence Class rocks in the Columbia Hills, the overall Fe mineralogical compositions and similar basaltic bulk chemical compositions (calculated with respect to S = Cl = 0) of the population of altered rocks analyzed by MER imply isochemical alteration of basaltic precursors at low water-to-rock ratios.

Morris, Richard V.↗

Fe-Bearing Phases Identified by the Moessbauer Spectrometers on the Mars Exploration Rovers: An Overview

The twin Mars Exploration Rovers Spirit and Opportunity have explored the martian surface at Gusev Crater (GC) and Meridiani Planum (MP), respectively, for about two Earth years. The Moessbauer (MB) spectrometers on both rovers have analyzed an aggregate of ~200 surface targets and have returned to Earth information on the oxidation state of iron, the mineralogical composition of Febearing phases, and the distribution of Fe among oxidation states and phases at the two landing sites [1-7]. To date, 15 component subspectra (10 doublets and 5 sextets) have been identified and most have been assigned to mineralogical compositions. Two subspectra are assigned to phases (jarosite and goethite) that are marker minerals for aqueous processes because they contain hydroxide anion in their structures. In this paper, we give an overview of the Febearing phases identified and their distributions at Gusev crater and Meridiani Planum.

Morris, R. V.↗