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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Reduction of Hg II by Mn II

The reduction of Hg II to Hg I or Hg 0 can lead to significant changes in Hg toxicity and mobility in the environment. Photochemical reduction is the primary process for the reduction of Hg II to Hg 0 in sunlit environments; however, dark reduction of HgII can occur via microbial metabolic processes and/or reduction by reduced natural organic matter, Fe II mineral phases, Fe II sorbed to minerals, or aqueous Fe II . Here, in this study, we demonstrate a novel Hg II reduction pathway involving another environmentally relevant reductant, Mn II . Abiotic reduction of Hg II O by Mn II was studied as a function of pH and anion environment (perchlorate, sulfate, chloride) using X-ray absorption spectroscopy to characterize the solid-phase Hg and Mn species. At circumneutral pH of 7.5, about 70% of Hg II was reduced to elemental Hg 0 within 2 h. In contrast, 12 h were needed to achieve the same extent of reduction at pH 6.9. In the presence of sulfate and chloride, Hg I species were formed. Hg II reduction was initially rapid and coupled with the oxidation of soluble Mn II -oxides to insoluble Mn IV -oxides, followed by a significantly slower reduction of Hg II during the Mn II -catalyzed transformation of the Mn IV -oxides to hydroxide and oxyhydroxide minerals. The observed reduction of Hg II by Mn II at circumneutral pH could be an important transformation pathway for environmental Hg, affecting its bioavailability and mobility under mildly reducing conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Proton-Coupled Electron Transfer Mechanisms for CO 2 Reduction to Methanol Catalyzed by Surface-Immobilized Cobalt Phthalocyanine

Immobilized cobalt phthalocyanine (CoPc) is a highly promising architecture for the six-proton, six-electron reduction of CO 2 to methanol. This electroreduction process relies on proton-coupled electron transfer (PCET) reactions that can occur by sequential or concerted mechanisms. Immobilization on a conductive support such as carbon nanotubes or graphitic flakes can fundamentally alter the PCET mechanisms. We use density functional theory (DFT) calculations of CoPc adsorbed on an explicit graphitic surface model to investigate intermediates in the electroreduction of CO 2 to methanol. Our calculations show that the alignment of the CoPc and graphitic electronic states influences the reductive chemistry. These calculations also distinguish between charging the graphitic surface and reducing the CoPc and adsorbed intermediates as electrons are added to the system. This analysis allows us to identify the chemical transformations that are likely to be concerted PCET, defined for these systems as the mechanism in which protonation of a CO 2 reduction intermediate is accompanied by electron abstraction from the graphitic surface to the adsorbate without thermodynamically stable intermediates. Furthermore, this work establishes a mechanistic pathway for methanol production that is consistent with experimental observations and provides fundamental insight into how immobilization of the CoPc impacts its CO 2 reduction chemistry.

Adsorption↗
NASA NTRS2017

Sample Processor for Life on Icy Worlds (SPLIce): Design and Test Results

We report the design, development, and testing of the Sample Processor for Life on Icy Worlds (SPLIce) system, a microfluidic sample processor to enable autonomous detection of signatures of life and measurements of habitability parameters in Ocean Worlds. This monolithic fluid processing-and-handling system (Figure 1; mass 0.5 kg) retrieves a 50-L-volume sample and prepares it to supply a suite of detection instruments, each with unique preparation needs. SPLIce has potential applications in orbiter missions that sample ocean plumes, such as found in Saturns icy moon Enceladus, or landed missions on the surface of icy satellites, such as Jupiters moon Europa. Answering the question Are we alone in the universe? is captivating and exceptionally challenging. Even general criteria that define life very broadly include a significant role for water [1,2]. Searches for extinct or extant life therefore prioritize locations of abundant water whether in ancient (Mars), or present (Europa and Enceladus) times. Only two previous planetary missions had onboard fluid processing: the Viking Biology Experiments [3] and Phoenixs Wet Chemistry Laboratory (WCL) [4]. SPLIce differs crucially from those systems, including its capability to process and distribute L-volume samples and the integration autonomous control of a wide range of fluidic functions, including: 1) retrieval of fluid samples from an evacuated sample chamber; 2) onboard multi-year storage of dehydrated reagents; 3) integrated pressure, pH, and conductivity measurement; 4) filtration and retention of insoluble particles for microscopy; 5) dilution or vacuum-driven concentration of samples to accommodate instrument working ranges; 6) removal of gas bubbles from sample aliquots; 7) unidirectional flow (check valves); 8) active flow-path selection (solenoid-actuated valves); 9) metered pumping in 100 nL volume increments. The SPLIce manifold, made of three thermally fused layers of precision-machined cyclo-olefin polymer, supports all fluidic components (Figure 1) and integrated microchannels (125 x 250 m). Fluid is pumped by a stepper-motor-driven pump (Lee Co.). The functionality of the integrated MEMS pressure sensor (Honeywell) and passive check valves (Figure 2) were tested in conjunction with our newly designed integral bubble traps (Figure 3) and hydrophobic membrane-based concentrator (Figure 4). The concentrator (initially tested as a standalone component) demonstrated 5-fold vacuum-evaporative concentration. Polyethylene fused bead beds (PEFBBs; 50 porosity) store drylyophilized buffers, calibrants, and fluorescent dyes, and also promote mixing of sample with calibrant, dye, or H2O. Software-controlled automated tests demonstrated successful 1) fluid delivery to each component 2) valve and pump synchronization 3) sample aliquot delivery to instrument interface ports, and 4) rehydration of vacuum-dried fluorescent dye. In Figure 5, fluorescein on PEFBBs was rehydrated for 15 min using a pump-delivered water aliquot; it is displaced as H2O enters the bottom of the channel and pushes the dye into a check valve. Ultimately, SPLIce will fluorescently label amino acids in the sample for microchip-based electrophoretic (MCE) chiral separation and detection to seek and quantify key organic bio-signatures [5]; it will also deliver sample to a microfluidic version of WCL (mWCL) to measure soluble ions and redox-active species.

Life detection↗
NASA NTRSDate not supplied

Multi-Anvil Experimentation Applied to Planetary Differentiation

Planets undergo differentiation that includes segregation of metal from silicate at high temperatures and pressures ranging from deep planetary core pressures (>300 GPa for Earth)to very shallow conditions of asteroids (<100 MPa).The multi-anvil solid media apparatus accesses the middle part of this range from 3 to 30 GPa –pressure relevant to the interior of Mercury, Venus, Earth, Earth’s Moon, and Mars. Early planets are thought to have experienced high temperatures from a combination of heat sources including radioactive decay, gravitational and accretional heating, and impact processes. These heating events led to melting of mantles and cores, thus requiring an understanding of solid-liquid equilibria in metal-silicate systems. In 2006 we established a multi-anvil facility at NASA-JSC combining an 880 ton press and a Kawai/Walker type module from Rockland Research. Our high PT work has been greatly facilitated by use of the COMPRES multi-anvil assemblies (1). Our recent work has included studies of element partitioning between liquid metal and liquid silicate(e.g., 2), as well as between minerals and melts(e.g., 3), both of which have led to better constraints on the timing and conditions of planetary differentiation(e.g. 4). Several examples involving sustained efforts will be summarized below and for the presentation. The distribution of siderophile (iron-loving) elements between core and mantle is controlled by metal-silicate equilibrium across a wide range of pressures. Therefore, experimentation across this pressure range helps to calibrate elemental partitioning models that can be applied to planets, and used to predict mantle chemistry and composition during planetary differentiation. Our studies have focused on a wide range of siderophile elements (refractory Ni, Co, W, Mo; volatile P, Ga, Cu, Sn, Sb; highly siderophile Au, Pd) that have constrained partitioning, valence, and isotopic fractionation, and applied to Earth, Moon, and Mars. When molten mantles (magma oceans) cool enough to initiate crystallization, the solids precipitate at depth and in large planets this involves high pressure phases like garnet, majorite, akimotoite, and ringwoodite. As these solids precipitate they can segregate from liquid by density contrasts, thus causing elemental fractionation which can be used to decipher timing of differentiation. Mineral/melt and metal/silicate equilibria in our lab have helped to better understand high pressure fractionation of isotopic parent/daughter pairs Hf/W, Mn/Cr, Pd/Ag, Pt/Os, Re/Os, and U/Pb, and their application to Earth, Moon and Mars. There remains great potential for multi-anvil experimentation to shed light on many pressure–dependent aspects of planetary evolution such as core formation, high pressure phase equilibria, redox equilibria, and volatile evolution and storage. References1. Leinenweber, K., et al.(2012) American Mineralogist,97, 353–368. 2.Righter, K., et al.(2020) Geochem. Persp. Lett.15, 1-6.3. Righter, K., et al.(2020) Met. Planet. Sci 55, 2741-2757.4. Righter, K., et al.(2020)Earth and Planetary Science Letters,552, 116590.

pressure↗
NASA NTRS2013

New Class of Flow Batteries for Terrestrial and Aerospace Energy Storage Applications

Future sustainable energy generation technologies such as photovoltaic and wind farms require advanced energy storage systems on a massive scale to make the alternate (green) energy options practical. The daunting requirements of such large-scale energy systems such as long operating and cycle life, safety, and low cost are not adequately met by state-of-the-art energy storage technologies such as vanadium flow cells, lead-acid, and zinc-bromine batteries. Much attention is being paid to redox batteries specifically to the vanadium redox battery (VRB) due to their simplicity, low cost, and good life characteristics compared to other related battery technologies. NASA is currently seeking high-specific- energy and long-cycle-life rechargeable batteries in the 10-to-100-kW range to support future human exploration missions, such as planetary habitats, human rovers, etc. The flow batteries described above are excellent candidates for these applications, as well as other applications that propose to use regenerative fuel cells. A new flow cell technology is proposed based on coupling two novel electrodes in the form of solvated electron systems (SES) between an alkali (or alkaline earth) metal and poly aromatic hydrocarbons (PAH), separated by an ionically conducting separator. The cell reaction involves the formation of such SES with a PAH of high voltage in the cathode, while the alkali (or alkaline earth metal) is reduced from such an MPAH complex in the anode half-cell. During recharge, the reactions are reversed in both electrodes. In other words, the alkali (alkaline earth) metal ion simply shuttles from one M-PAH complex (SES) to another, which are separated by a metal-ion conducting solid or polymer electrolyte separator. As an example, the concept was demonstrated with Li-naphthalene//Li DDQ (DDQ is 2,3-Dichloro-5,6-dicyano- 1,4-benzoquinone) separated by lithium super ion conductor, either ceramic or polymer (solid polymer or gel polymer) electrolytes. The reactants are Li-naphthalene dissolved in tetrahydrofuran (THF) with a lithium salt of 1M LiBF4 (lithium tetra fluoroborate) in the anode compartment, and DDQ again dissolved in THF and also containing 1M LiBF4 salt in the cathode half-cell. The solid electrolyte separator used in the first set of experiments is a ceramic solid electrolyte, available from a commercial source. The open circuit voltage of the cells is close to 3.0 V, as expected from the individual half-cell voltages of Li-naphthalene and Li-DDQ. Upon discharge, the cell shows steady discharge voltage of 2.7 V, which confirms that the electrochemical processes do involve lithium ion shuttling from the anodic compartment to the cathode half-cell. The reversibility or rechargeability is demonstrated by charging the partially discharged cells (i.e., with lithium present in the DDQ half). Once again, a steady voltage close to 3.0 V was observed during charge, indicating that the system is quite reversible. In the subsequent concept-demonstration studies, the ceramic electrolyte has been replaced with a gel polymer electrolyte, e.g., PVDF-HFP (poly vinylene difluoride hexafluoropropene) gel, which has several advantages such as high ionic conductivity (almost comparable to liquid electrolyte and about 2 orders of magnitude better than the ceramic equivalent), lower cost, and possibly higher chemical stability at the anode. In addition, it can be bonded to the electrode by thermal fusion to form membrane electrode assemblies (MEAs), as is done in fuel cells.

Bugga, Ratnakumar V.↗
DOE OSTI2017

Coordination chemistry controls the thiol oxidase activity of the B 12 -trafficking protein CblC

The cobalamin or B 12 cofactor supports sulfur and one-carbon metabolism and the catabolism of odd-chain fatty acids, branched-chain amino acids, and cholesterol. CblC is a B 12 -processing enzyme involved in an early cytoplasmic step in the cofactor-trafficking pathway. It catalyzes the glutathione (GSH)-dependent dealkylation of alkylcobalamins and the reductive decyanation of cyanocobalamin. CblC from Caenorhabditis elegans (ceCblC) also exhibits a robust thiol oxidase activity, converting reduced GSH to oxidized GSSG with concomitant scrubbing of ambient dissolved O2. The mechanism of thiol oxidation catalyzed by ceCblC is not known. In this study, we demonstrate that novel coordination chemistry accessible to ceCblC-bound cobalamin supports its thiol oxidase activity via a glutathionyl-cobalamin intermediate. Deglutathionylation of glutathionyl-cobalamin by a second molecule of GSH yields GSSG. The crystal structure of ceCblC provides insights into how architectural differences at the α- and β-faces of cobalamin promote the thiol oxidase activity of ceCblC but mute it in wild-type human CblC. The R161G and R161Q mutations in human CblC unmask its latent thiol oxidase activity and are correlated with increased cellular oxidative stress disease. In summary, we have uncovered key architectural features in the cobalamin-binding pocket that support unusual cob(II)alamin coordination chemistry and enable the thiol oxidase activity of ceCblC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Soil properties and sediment accretion modulate methane fluxes from restored wetlands

Wetlands are the largest source of methane (CH 4 ) globally, yet our understanding of how process-level controls scale to ecosystem fluxes remains limited. It is particularly uncertain how variable soil properties influence ecosystem CH 4 emissions on annual time scales. Here. we measured ecosystem carbon dioxide (CO 2 ) and CH 4 fluxes by eddy covariance from two wetlands recently restored on peat and alluvium soils within the Sacramento–San Joaquin Delta of California. Annual CH 4 fluxes from the alluvium wetland were significantly lower than the peat site for multiple years following restoration, but these differences were not explained by variation in dominant climate drivers or productivity across wetlands. Soil iron (Fe) concentrations were significantly higher in alluvium soils, and alluvium CH 4 fluxes were decoupled from plant processes compared with the peat site, as expected when Fe reduction inhibits CH 4 production in the rhizosphere. Soil carbon content and CO 2 uptake rates did not vary across wetlands and, thus, could also be ruled out as drivers of initial CH 4 flux differences. Differences in wetland CH 4 fluxes across soil types were transient; alluvium wetland fluxes were similar to peat wetland fluxes 3 years after restoration. Changing alluvium CH 4 emissions with time could not be explained by an empirical model based on dominant CH 4 flux biophysical drivers, suggesting that other factors, not measured by our eddy covariance towers, were responsible for these changes. Recently accreted alluvium soils were less acidic and contained more reduced Fe compared with the pre-restoration parent soils, suggesting that CH 4 emissions increased as conditions became more favorable to methanogenesis within wetland sediments. This study suggests that alluvium soil properties, likely Fe content, are capable of inhibiting ecosystem-scale wetland CH 4 flux, but these effects appear to be transient without continued input of alluvium to wetland sediments.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Catalytic Reduction of Carbon Monoxide to Liquid Fuels with Recyclable Hydride Donors

Solar light absorption and catalysis are physically separated processes in natural photosynthesis. Natural cofactors, such as nicotinamide adenine dinucleotides (NADH), transport electrons and hydrogen to regulate and activate enzymes at remote locations. The physical separation of light absorption from catalysis provides some inspiration for artificial photosynthesis. One rather extreme implementation is to use copper wires to transport carriers from photovoltaic cells to dark electrodes, where catalysis occurs. Indeed, with a futuristic electrical grid powered solely by photovoltaics, solar capture could be separated from catalysis by hundreds of miles. An alternative approach, that bares more similarity to natural photosynthesis, employs mobile NADH/NAD + -like species that shuttle between the light absorber and a proximate, yet unilluminated, location where catalysis occurs. Additionally, such a remote approach to solar photocatalysis was recently proposed for the reduction of carbon oxides, CO 2 and CO, to methanol by cascade catalysis. This developing artificial photosynthetic approach offers the promise of catalytic generation of methanol and oxygen gas with sunlight as the sole energy source and CO 2 and water as the only chemical feedstocks. This Viewpoint evaluates the strengths and weaknesses of this approach with an emphasis on CO reduction catalysis with photorecyclable hydride donors while looking forward to what might reasonably be achieved with continued research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Nitrate Reduction Modeling under Acidic Conditions with Late Transition Metals

The electrochemical reduction of nitrate (NO 3 R) to ammonia is a bold yet conceivable way of producing ammonia using renewable electricity. However, serious challenges remain in finding optimal electrocatalysts for the process. An atomistic understanding of the surface energetics behind the NO 3 R is needed in order to design an efficient catalyst. Herein, we combine energetics from density functional theory and microkinetic modeling to demonstrate how surface descriptors can help simplify the search for efficient NO 3 R electrocatalysts. We illustrate the strong correlations between transition-state energetics and O* binding energies for adsorbed nitrate and nitrite on transition metals. For intermediates from NO* and beyond, we compare the benefits of using either the N* or H* binding energies to predict reduction onset potentials. These insights enable us to develop a simple microkinetic model that elucidates the surface coverages of intermediates and the product selectivity of NO 3 R across a range of potentials and transition metals. As a result, we show that the model adequately corroborates with quasi-steady-state rates observed experimentally.

ammonia↗
DOE OSTI2023

Lithium superoxide-based high rate Li-Air batteries enabled by Di-iridium sulfur bridge active sites

Li-oxygen (Li-O 2 ) batteries can potentially provide much higher energy density than Li-ion batteries; however, the practical application of these batteries is hindered due to several drawbacks such as low current rates and high overpotential for the charging process. Here, in this paper, we report a novel Li-Air battery system that operates under high current rates (up to 1mAcm -2 ) with LiO 2 as the primary discharge product instead of the commonly reported Li 2 O 2 . This LiO 2 based battery at high rates is through a combination of an as-synthesized new one-dimensional (1D) transition metal trichalcogenide mid-entropy alloy of SnIrS 3.6 as a cathode catalyst and an electrolyte blend with a SnI 2 bi-functional additive. It is revealed that SnIrS 3.6 has a microporous structure composed of six- and five-coordinated metal atoms, forming octahedral and triangular bipyramids which has not been observed in other layered chalcogeide materials. DFT calculations reveal that the SnIrS 3.6 structure can result in LiO 2 formation through di-iridium sulfur bridge active sites that results in strong binding of O 2 and LiO 2 preventing disproportionation to Li 2 O 2 and enabling high rates. This finding will open a new perspective in designing advanced LiO 2 -based Li-O 2 batteries for real practices.

25 ENERGY STORAGE↗
NASA NTRSDate not supplied

Initial analysis of “stone” size Ryugu samples: current status

As a part of the initial analysis of the Ryugu samples, we perform a variety of analyses of millimeter-sized "stones". Our goals are to elucidate the entire formation process of C-type asteroid Ryugu from the viewpoint of petrology and mineralogy ande obtain necessary information by sample analysis, and then simulate the formation of Ryugu based on the evidencef obtained rom sample analysis. Eighteen stones (8 from Room A and 10 from Room C) were received from the ISAS curation facility on June 1, 2021, and brought into a fully nitrogen-displaced glove box at Tohoku University. At the same time, we also received the powder samples from Room A and Room C. To completely block the atmosphere from leaking into the container, all samples were put in the sample transport containers prepared by ISAS, transferred from the main chamber to the glovebox at ISAS, and then all containers were completely sealed in plastic bags with moisture and oxygen absorbers. No moisture or oxygen was detected when the bags were opened in the glove box at Tohoku University, so it was confirmed that there was no exposure to the atmosphere during transport. To date, a number of analyses have been carried out successfully and almost on schedule. The analysis started with the measurement of reflectance spectra, which are sensitive to atmospheric oxidation, hydroxylation, and adsorbed water. The visible, near-infrared, and mid-infrared reflectance spectra were measured while the samples were kept airtight. The spectra of powder samples and stone samples (as aggregates and as single stone) were successfully obtained. A major feature of the stone team's analysis is the use of synchrotron radiation facilities around the world. Since this analysis is non-destructive, stone samples whose reflectance spectra were measured were sent to KEK, SPring-8, ESRF (France), SOLEIL (France), DESY (Germany), and APS (USA). Using these synchrotron radiation facilities, high spatial resolution and sensitivity XRD, STXM, XANES, CT [1], IR-CT, FT-IR [2, 3], XRF, and Mössbauer analyses were performed. Most of the analyses were carried out under air-tight conditions on the stone samples and the particulates separated from the stone samples. These analyses allowed us to determine the three-dimensional distribution of minerals and elements, redox state, density and porosity of the stone samples. Furthermore, as a characteristic analysis of the stone team, light elemental analysis using negative Muon was performed at the MLF facility of J-PARC with an exceptionally long allocation of machine time. This is the only non-destructive method to measure the concentration of light elements in the whole (not the surface) of stone samples. Because the characteristic X-rays produced by muon irradiation are much higher in energy than the fluorescent X-rays produced by X-ray irradiation, there is little effect of self-absorption by the sample, and therefore, the concentration of light elements such as carbon, oxygen, and Na in the entire "stone" sample can be determined. Some stone samples are currently being measured for heat and strength physical properties in order to understand the physical properties of asteroid Ryugu. The data obtained from these measurements are useful for interpreting the remote-sensing data data taken from the surface layer of the asteroid Ryugu [4-7]. It is also important for understanding the behavior of the Ryugu material during impact events. The surfaces of many stone samples were observed by electron microscopy and other techniques, especially on natural “flat” surfaces formed on 5 stomes. As a result, characteristric mineral aggregates formed by the reactions with water and characteiristic impact features were observed on some of the samples. Based on the observations of surfaces and the synchrotron measurements of the whole stones, important objects such as characteristic structures and specific crystal aggregates for understanding the formation history of the asteroid were identified, and these parts were separated from the stone samples using an Xe beam (pFIB) and analyzed by various methods including transmission electron microscopy and synchrotron radiation analysis. Many stone samples, from which important objects have been separated, are embedded in epoxy resin and cut to produce many polished sections. Electron microscopy and spectroscopic measurements of the polished surfaces are being carried out to reveal the detailed mineralogical properties and elemental distribution inside the stone samples. In the fall, machine time for synchrotron radiation will begin, and we plan to analyze single crystals and characteristic objects separated from the stone samples.

Tomoki Nakamura↗
DOE OSTI2022

Continuum Modeling of Porous Electrodes for Electrochemical Synthesis

Electrochemical synthesis possesses substantial promise to utilize renewable energy sources to power the conversion of abundant feedstocks to value-added commodity chemicals and fuels. Of the potential system architectures for these processes, only systems employing 3-D structured porous electrodes have the capacity to achieve the high rates of conversion necessary for industrial scale. However, the phenomena and environments in these systems are not well understood and are challenging to probe experimentally. Fortunately, continuum modeling is well-suited to rationalize the observed behavior in electrochemical synthesis, as well as to ultimately provide recommendations for guiding the design of next-generation devices and components. In this review, we begin by presenting an historical review of modeling of porous electrode systems, with the aim of showing how past knowledge of macroscale modeling can contribute to the rising challenge of electrochemical synthesis. We then present a detailed overview of the governing physics and assumptions required to simulate porous electrode systems for electrochemical synthesis. Here, leveraging the developed understanding of porous-electrode theory, we survey and discuss the present literature reports on simulating multiscale phenomena in porous electrodes in order to demonstrate their relevance to understanding and improving the performance of devices for electrochemical synthesis. Lastly, we provide our perspectives regarding future directions in the development of models that can most accurately describe and predict the performance of such devices and discuss the best potential applications of future models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Direct Evidence of Visible Light-Induced Homolysis in Chlorobis(2,9-dimethyl-1,10-phenanthroline)copper(II)

Developments in the field of photoredox catalysis that leveraged the long-lived excited states of Ir(III) and Ru(II) photosensitizers to enable radical coupling processes paved the way for explorations of synthetic transformations that would otherwise remain unrealized. While first row transition metal photocatalysts have not been as extensively investigated, valuable synthetic transformations covering broad scopes of olefin functionalization have been recently reported featuring photoactivated chlorobis(phenanthroline) Cu(II) complexes. In this study, the photochemical processes underpinning the catalytic activity of [Cu(dmp) 2 Cl]Cl (dmp = 2,9-dimethyl-1,10-phenanthroline) were studied. The combined results from static spectroscopic measurements and conventional photochemistry, ultrafast transient absorption, and electron paramagnetic resonance spin trapping experiments strongly support blue light (λ ex = 427 or 470 nm)-induced Cu–Cl homolytic bond cleavage in [Cu(dmp) 2 Cl] + occurring in <100 fs. On the basis of electronic structure calculations, this bond-breaking photochemistry corresponds to the Cl → Cu(II) ligand-to-metal charge transfer transition, unmasking a Cu(I) species [Cu(dmp) 2 ] + and a Cl atom, thereby serving as a departure point for both Cu(I)- or Cu(II)-based photoredox transformations. No net photochemistry was observed through direct excitation of the ligand-field transitions in the red (λ ex = 785 or 800 nm), and all combined experiments indicated no evidence of Cu–Cl bond cleavage under these conditions. As a result, the underlying visible light-induced homolysis of a metal–ligand bond yielding a one-electron-reduced photosensitizer and a radical species may form the basis for novel transformations initiated by photoinduced homolysis featuring in situ-formed metal–substrate adducts utilizing first row transition metal complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Oxidative Alteration of Ferrous Smectites and Implications for the Redox Evolution of Early Mars: Oxidation Products of Ferrous Smectites

Surface conditions on early Mars were likely anoxic, similar to early Earth, but the timing of the evolution to oxic conditions characteristic of contemporary Mars is unresolved. Ferrous trioctahedral smectites are the thermodynamically predicted products of anoxic basalt weathering, but orbital analyses of Noachian-aged terrains find primarily Fe 3+ -bearing clay minerals. Rover-based detection of Fe 2+ -bearing trioctahedral smectites at Gale Crater suggests that ferrous smectites are the unoxidized progenitors of orbitally detected ferric smectites. To assess this pathway, we conducted ambient-temperature oxidative alteration experiments on four synthetic ferrous smectites having molar Fe/(Mg + Fe) from 1.00 to 0.33. Smectite suspension in air-saturated solutions produced incomplete oxidation (24–38% Fe 3+ /ΣFe). Additional smectite oxidation occurred upon reexposure to air-saturated solutions after anoxic hydrothermal recrystallization, which accelerated cation and charge redistribution in the octahedral sheet. Oxidation was accompanied by contraction of the octahedral sheet (d (060) decreased from 1.53–1.56 Å to 1.52 Å), consistent with a shift toward dioctahedral structure. Ferrous smectite oxidation by aqueous hydrogen peroxide solutions resulted in nearly complete Fe 2+ oxidation but also led to partial Fe 3+ ejection from the structure, producing nanoparticulate hematite. Reflectance spectra of oxidized smectites were characterized by (Fe 3+ ,Mg) 2 -OH bands at 2.28–2.30 μm, consistent with oxidative formation of dioctahedral nontronite. Accordingly, ferrous smectites are plausible precursors to observed ferric smectites on Mars, and their presence in late-Noachian sedimentary units suggests that anoxic conditions may have persisted on Mars beyond the Noachian.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Dynamic Stabilization of Metal Oxide–Water Interfaces

The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe 2 O 3 ) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the structure of the ($1\bar{10}2 $) termination is dynamically stabilized by picosecond water exchange. Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locations and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies. Frequent water exchange occurs even for an ultrathin adsorbed water film persisting on the surface under a dry atmosphere. The resulting time-averaged interfacial structure consists of a ridged lateral arrangement of adsorbed water molecules hydrogen bonded to terminal aquo groups. Surface pK a prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface. Our findings provide important new insights for understanding complex interfacial chemical processes at metal oxide–water interfaces.

58 GEOSCIENCES↗
NASA NTRS1993

The nanophase iron mineral(s) in Mars soil

A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.

NASA Program Exobiology↗
DOE OSTI2021

Catalase protects against nonenzymatic decarboxylations during photorespiration in Arabidopsis thaliana

Abstract Photorespiration recovers carbon that would be otherwise lost following the oxygenation reaction of rubisco and production of glycolate. Photorespiration is essential in plants and recycles glycolate into usable metabolic products through reactions spanning the chloroplast, mitochondrion, and peroxisome. Catalase in peroxisomes plays an important role in this process by disproportionating H 2 O 2 resulting from glycolate oxidation into O 2 and water. We hypothesize that catalase in the peroxisome also protects against nonenzymatic decarboxylations between hydrogen peroxide and photorespiratory intermediates (glyoxylate and/or hydroxypyruvate). We test this hypothesis by detailed gas exchange and biochemical analysis of Arabidopsis thaliana mutants lacking peroxisomal catalase. Our results strongly support this hypothesis, with catalase mutants showing gas exchange evidence for an increased stoichiometry of CO 2 release from photorespiration, specifically an increase in the CO 2 compensation point, a photorespiratory‐dependent decrease in the quantum efficiency of CO 2 assimilation, increase in the 12 CO 2 released in a 13 CO 2 background, and an increase in the postillumination CO 2 burst. Further metabolic evidence suggests this excess CO 2 release occurred via the nonenzymatic decarboxylation of hydroxypyruvate. Specifically, the catalase mutant showed an accumulation of photorespiratory intermediates during a transient increase in rubisco oxygenation consistent with this hypothesis. Additionally, end products of alternative hypotheses explaining this excess release were similar between wild type and catalase mutants. Furthermore, the calculated rate of hydroxypyruvate decarboxylation in catalase mutant is much higher than that of glyoxylate decarboxylation. This work provides evidence that these nonenzymatic decarboxylation reactions, predominately hydroxypyruvate decarboxylation, can occur in vivo when photorespiratory metabolism is genetically disrupted.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Pressurized Gas-Driven Elemental Redistribution Enables Ultrastable PtNi Catalysts for Heavy-Duty Vehicles

Gas-driven element redistribution, characterized by the preferential enrichment of one element at the surface relative to the bulk, is frequently observed in multicomponent alloys. Using L1 0 -ordered PtNi as a model system, we reveal that gas pressure plays a critical role in governing adsorption-driven surface composition during annealing in reducing gases: low pressure favors Pt surface segregation, while high pressure facilitates Ni surface enrichment. In this study, we developed a high-pressure nitriding (HPN) strategy that modulates the surface structure and composition of PtNi catalysts. The resulting HPN-PtNi exhibits enhanced performance and durability in membrane electrode assemblies for heavy-duty fuel cell applications, maintaining a high current density of 1.19 A cm −2 at 0.7 V after 90,000 voltage cycles. Through a combination of experimental and theoretical analyses, we reveal that the HPN process forms additional stabilizing Ni−N bonds and induces elemental redistribution with Ni surface enrichment and a Ni-deficient Pt subsurface. These modifications alter the atomic coordination environment of the ordered PtNi phase. This work presents a generalizable strategy to design robust and high-performing Pt-based catalysts by controlling gas-pressure-driven elemental redistribution and dopant incorporation.

30 DIRECT ENERGY CONVERSION↗