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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Unraveling Electronic and Vibrational Coherences Following a Charge Transfer Process in a Photosystem II Reaction Center

A reaction center is a unique biological system that performs the initial charge separation within a Photosystem II (PSII) multiunit enzyme, which eventually drives the catalytic water-splitting in plants and algae. The possible role of quantum coherences coinciding with the energy and charge transfer processes in PSII reaction center is one of the active areas of research. Here, we study these quantum coherences by using a numerically exact method on an excitonic dimer model, including linear vibronic coupling and employing optimal parameters from experimental two-dimensional coherent spectroscopic measurements. This enables us to precisely capture the excitonic interaction between pigments and the dissipation of the energy from electronic and charge-transfer (CT) states to the protein environment. We employ the time nonlocal (TNL) quantum master equation to calculate the population dynamics, which yields numerically reliable results. The calculated results show that, due to the strong dissipation, the lifetime of electronic coherence is too short to have direct participation in the charge transfer processes. However, there are long-lived vibrational coherences present in the system at frequencies close to the excitionic energy gap. These are strongly coupled with the electronic coherences, which makes the detection of the electronic coherences with conventional techniques very challenging. Additionally, we unravel the strong excitonic interaction of radical pair (PD1 and PD2) in the reaction center, which results in a long-lived electronic coherence of >100 fs, even at room temperature. Our work provide important physical insight to the charge separation process in PSII reaction center, which may be helpful for better understanding of photophysical processes in other natural and artificial light-harvesting systems.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2024

Unveiling the Role of Surface Ir-Oxo Species in O 2 Evolution at IrO 2 Electrocatalysts via Embedded Cluster Multireference Calculations

Understanding the mechanisms driving the oxygen evolution reaction (OER) on iridium oxide (IrO 2 )-based catalysts is essential to improving their performance and enabling an actual scale-up of water-splitting photoelectrochemical cells. The mechanistic pathways at IrO 2 interfaces have been extensively investigated computationally using density functional theory (DFT), which predicts a high-energy barrier for the last step of the OER of molecular oxygen detachment and release from the catalyst surface. Nevertheless, surface O 2 over- and under-binding results by standard generalized gradient approximation and hybrid density functionals, respectively, call for further analysis of this crucial step via multireference methods. Aiming at unveiling the nature of such a barrier, we hereby address the formation of O 2 from the most-stable IrO 2 (110) surface with both periodic DFT and an electrostatic embedded cluster approach at the n-electron valence-state perturbation theory. With this multireference approach, we find a value for the aforementioned energy barrier that is much closer to experimental indications than DFT ones. Here, an in-depth analysis of the involved molecular orbitals suggests that the origin of this barrier is related to the breaking of a π interaction between O 2 and Ir surface atom and to a significant additional O 2 interaction with adjacent electrophilic Ir-oxo species, which is present under experimental operating conditions. Besides shedding light on the mechanism of the OER on IrO 2 , these findings point out the importance of multireference methods for dissecting complex reactions at electrocatalytic interfaces and pave the route for further investigations with effective embedding approaches.

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

DESI DR1 Ly$α$ forest: 3D full-shape analysis and cosmological constraints

We perform an analysis of the full shapes of Lyman-$α$ (Ly$α$) forest correlation functions measured from the first data release (DR1) of the Dark Energy Spectroscopic Instrument (DESI). Our analysis focuses on measuring the Alcock-Paczynski (AP) effect and the cosmic growth rate times the amplitude of matter fluctuations in spheres of $8$$h^{-1}\text{Mpc}$, $fσ_8$. We validate our measurements using two different sets of mocks, a series of data splits, and a large set of analysis variations, which were first performed blinded. Our analysis constrains the ratio $D_M/D_H(z_\mathrm{eff})=4.525\pm0.071$, where $D_H=c/H(z)$ is the Hubble distance, $D_M$ is the transverse comoving distance, and the effective redshift is $z_\mathrm{eff}=2.33$. This is a factor of $2.4$ tighter than the Baryon Acoustic Oscillation (BAO) constraint from the same data. When combining with Ly$α$ BAO constraints from DESI DR2, we obtain the ratios $D_H(z_\mathrm{eff})/r_d=8.646\pm0.077$ and $D_M(z_\mathrm{eff})/r_d=38.90\pm0.38$, where $r_d$ is the sound horizon at the drag epoch. We also measure $fσ_8(z_\mathrm{eff}) = 0.37\; ^{+0.055}_{-0.065} \,(\mathrm{stat})\, \pm 0.033 \,(\mathrm{sys})$, but we do not use it for cosmological inference due to difficulties in its validation with mocks. In $Λ$CDM, our measurements are consistent with both cosmic microwave background (CMB) and galaxy clustering constraints. Using a nucleosynthesis prior but no CMB anisotropy information, we measure the Hubble constant to be $H_0 = 68.3\pm 1.6\;\,{\rm km\,s^{-1}\,Mpc^{-1}}$ within $Λ$CDM. Finally, we show that Ly$α$ forest AP measurements can help improve constraints on the dark energy equation of state, and are expected to play an important role in upcoming DESI analyses.

Cuceu, Andrei [LBL, Berkeley; Chicago U., KICP] (O↗
DOE OSTI2025

Deletion of Re -citrate synthase allows for analysis of contributions of tricarboxylic acid cycle directionality to the growth of Heliomicrobium modesticaldum

ABSTRACT Heliomicrobium modesticaldum,a phototrophic member of the phylum Firmicutes and family Clostridiales, possesses most of the enzymes specific to the reductive tricarboxylic acid (rTCA) cycle, except for the key enzyme, ATP-citrate lyase. It is thought to utilize a split TCA cycle when growing on pyruvate as a carbon source, in which the oxidative TCA (oTCA) direction generates most of the 2-ketoglutarate, but some can be produced in the reductive direction. Although a typicalSi-citrate synthase gene is not found in the genome, it was suggested that gene HM1_2993, annotated as homocitrate synthase, actually encodesRe-citrate synthase, which would function as the initial enzyme of the oTCA cycle. We deleted this gene to test this hypothesis and, if true, see what effect severing access to the oTCA cycle would have on this organism. The endogenous CRISPR-Cas system was used to replace the open reading frame with a selectable marker. The deletion mutants could grow on pyruvate but were unable to grow phototrophically on acetate + CO 2 as carbon source. Growth on acetate could be rescued by the addition of different electron sources (formate or ascorbate), suggesting that the oTCA cycle is used to oxidize acetate to generate electrons required to drive the carboxylation of acetyl-CoA. The deletion mutants were capable of growing in acetate minimal media without additional organic supplements beyond formate, demonstrating that the rTCA cycle can be employed to support sufficient 2-ketoglutarate production in this organism, unlike citrate synthase mutants in several chemoheterotrophic organisms utilizing the oTCA cycle. IMPORTANCE Heliobacteria are a unique group of phototrophic bacteria that are obligate anaerobes and possess a rudimentary system to use light as a source of energy. They do not make oxygen or fix carbon dioxide. Here, we explore their fundamental carbon metabolism to understand the role and operation of the central TCA cycle. This work shows both the role and operation of this cycle under different growth modes and explains how these organisms can obtain electrons to drive their biosynthetic metabolism. This foundational knowledge will be crucial in the future when attempts are made to use this organism as a platform for oxygen-sensitive synthesis of compounds in an anaerobe that can use light as its energy source.

Biotechnology & Applied Microbiology↗
DOE OSTI2020

Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes

Bipolar membranes (BPMs) have the potential to become critical components in electrochemical devices for a variety of electrolysis and electrosynthesis applications. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-electrolyzers. In this study, a continuum model of multi-ion transport in a BPM is developed and fit to experimental data. Specifically, concentration profiles are determined for all ionic species, and the importance of a water-dissociation catalyst is demonstrated. The model describes internal concentration polarization and co- and counter-ion crossover in BPMs, determining the mode of transport for ions within the BPM and revealing the significance of salt-ion crossover when operated with pH gradients relevant to electrolysis and electrosynthesis. Lastly, a sensitivity analysis reveals that the performance and lifetime of BPMs can be improved substantially by using of thinner dissociation catalysts, managing water transport, modulating the thickness of the individual layers in the BPM to control salt-ion crossover, and increasing the ion-exchange capacity of the ion-exchange layers in order to amplify the water-dissociation kinetics at the interface.

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

Water–Hydrocarbon Interactions in Anionic Pyrene Monohydrate

Interactions between water and polycyclic aromatic hydrocarbons are essential in many aspects of chemistry, from interstellar and atmospheric processes to interfacial hydrophobicity and wetting phenomena. Despite their growing importance, the intermolecular potentials of the water-hydrocarbon interactions are underdeveloped compared to water-water potentials, and there are similarly few experimental probes that are sensitive to the details of the water-hydrocarbon potential. We present a combined experimental and computational study of anionic pyrene monohydrate, one of the simplest water/hydrocarbon clusters. The action spectrum in the OH region of the mass-selected cluster ion provides a rigorous benchmark for intermolecular potentials and computational methodologies. We identify missing intermolecular interactions and shortcomings in conventional dynamics calculations by comparing experimental data to density functional theory and classical molecular dynamics calculations. Kinetic trapping is prevalent, even for one water molecule and one pyrene molecule, leading to slow equilibration in conventional molecular dynamics calculations, even on nanosecond timescales and at low temperatures (50 K). At constant energy, temperature fluctuations for the pair of molecules are substantial. Immersing the system in a bath of soft spheres and employing parallel tempering alleviates kinetic trapping and dampens temperature fluctuations, bringing the system closer to the thermodynamic limit. With such augmented sampling, a simple, flexible water model reproduces the linewidth and the asymmetric broadening of the symmetric OH stretching mode, which we assign to spectral diffusion. In the OH stretching region, dynamics calculations predict a more intense antisymmetric peak than experiments observe but do not predict the bimodal split symmetric peak that the experiments show. Furthermore, our work suggests that electronic polarization, missing in the empirical force field, is responsible for the first discrepancy and that quantum nuclear effects, captured neither in density functional theory nor in classical dynamics, may be responsible for the second.

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

Proton Scattering in NOvA Test Beam

The NuMI Off-axis $\nu_e$ Appearance (NOvA) experiment is a two-detector, long baseline, neutrino oscillation experiment, which aims to make a determination of the neutrino mass ordering, the octant of $\theta_{23}$, and measure possible charge-parity (CP) violation. Determining these parameters is a step towards answering some of the fundamental questions about neutrinos. Are neutrinos their own antiparticle? Could neutrinos be responsible for the matter-antimatter asymmetry of the universe? How do neutrinos get their mass? Answering these questions requires precise measurements of the parameters that govern how neutrinos behave, namely the mass squared splittings, mixing angles, and possible CP-violating phase factor in the PNMS matrix. Reaching high precision requires minimizing both statistical and systematic errors. As NOvA continues to accumulate data, the sizes of our statistical errors continue to shrink such that in a couple of years they will be comparable to our systematic errors. NOvA's current systematic errors are dominated by energy and calibration uncertainties. The Test Beam program was initiated to address these uncertainties by assessing the detector response in an environment where more parameters of the incoming particles are known. One of the main goals of the Test Beam program is to garner a better understanding of our systematic errors, particularly in energy measurement and detector response, so that the modeling of these parameters can be improved. I studied protons in the Test Beam Detector with momenta around \unit[1]{GeV/c}, the high end of the momentum range relevant to quasielastic neutrino interactions in NOvA. One question this sample can help to answer is if we correctly simulate the fraction of protons that have an inelastic scattering interaction versus ranging out. If protons inelastically scatter at different rates in our simulation and data, the correction applied to the hadronic system when reconstructing neutrino energy could be inaccurate, since events with inelastic scattering will have less visible energy in the detector. This is particularly important for quasielastic $\nu_\mu$ events, which have the lowest hadronic energy resolution, and therefore give us our best measurements of $\Delta m_{32}^2$ and $\theta_{23}$.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2023

Going around the Kok cycle of the water oxidation reaction with femtosecond X-ray crystallography

The water oxidation reaction in photosystem II (PS II) produces most of the molecular oxygen in the atmosphere, which sustains life on Earth, and in this process releases four electrons and four protons that drive the downstream process of CO 2 fixation in the photosynthetic apparatus. The catalytic center of PS II is an oxygen-bridged Mn 4 Ca complex (Mn 4 CaO 5 ) which is progressively oxidized upon the absorption of light by the chlorophyll of the PS II reaction center, and the accumulation of four oxidative equivalents in the catalytic center results in the oxidation of two waters to dioxygen in the last step. The recent emergence of X-ray free-electron lasers (XFELs) with intense femtosecond X-ray pulses has opened up opportunities to visualize this reaction in PS II as it proceeds through the catalytic cycle. In this review, we summarize our recent studies of the catalytic reaction in PS II by following the structural changes along the reaction pathway via room-temperature X-ray crystallography using XFELs. The evolution of the electron density changes at the Mn complex reveals notable structural changes, including the insertion of O X from a new water molecule, which disappears on completion of the reaction, implicating it in the O—O bond formation reaction. We were also able to follow the structural dynamics of the protein coordinating with the catalytic complex and of channels within the protein that are important for substrate and product transport, revealing well orchestrated conformational changes in response to the electronic changes at the Mn 4 Ca cluster.

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

Photo-scanning Electrochemical Microscopy Observation of Overall Water Splitting at a Single Aluminum-Doped Strontium Titanium Oxide Microcrystal

Particulate photocatalysts for the overall water-splitting (OWS) reaction offer promise as devices for hydrogen fuel generation. Even though such photocatalysts have been studied for nearly five decades, much of the understanding of their function is derived from observations of catalyst ensembles and macroscopic photoelectrodes. This is because the sub-micrometer size of most OWS photocatalysts makes spatially resolved measurements of their local reactivity very difficult. Here we employ photo-scanning electrochemical microscopy (photo-SECM) to quantitatively measure hydrogen and oxygen evolution at individual OWS photocatalyst particles for the first time. Micrometer-sized Al-doped SrTiO 3 /Rh 2-y Cr y O 3 photocatalyst particles were immobilized on a glass substrate and interrogated with a chemically modified SECM nanotip. The tip simultaneously served as a light guide to illuminate the photocatalyst and as an electrochemical nanoprobe to observe oxygen and hydrogen fluxes from OWS. Local O 2 and H 2 fluxes obtained from chopped light experiments and photo-SECM approach curves using a COMSOL Multiphysics finite-element model confirmed stoichiometric H 2 /O 2 evolution of 9.3/4.6 μmol cm -2 h -1 with no observable lag during chopped illumination cycles. Additionally, photoelectrochemical experiments on a single microcrystal attached to a nanoelectrode tip revealed a strong light intensity dependence of the OWS reaction. Here these results provide the first confirmation of OWS at single micrometer-sized photocatalyst particles. The developed experimental approach is an important step towards assessing the activity of photocatalyst particles at the nanometer scale.

25 ENERGY STORAGE↗
NASA NTRS1997

Constraints on the Nature and Distribution of Iridium Host Phases at the Cretaceous-Tertiary Boundary: Implications for Projectile Identity and dispersal on impact

Among Cretaceous-Tertiary boundary sites worldwide, variations in the concentrations and ratios of elements commonly enriched in meteorites complicate traditional geochemical attempts at impactor identification. Yet they may provide constraints on the physical and chemical processes associated with large-body disruption and dispersal, as well as with diagenesis of projectile components. To this end, we continue our efforts to identify the mineral host-phases of projectile-derived elements, particularly for Ir, and to document their partitioning between crater deposits and ejecta resulting from the Chicxulub basin-forming impact. Building on earlier work, we used INAA to measure Ir concentrations in successively smaller splits of finely powdered impact melt breccia from the Chicxulub Crater in Mexico (sample Y6Nl9-R(b)), and K/T boundary fish clay from Stevns Klint, Denmark (sample FC-1, split from 40 kg of homogenized material intended as an analytical standard). Results for the Chicxulub sample show a heterogeneous Ir distribution and document that at least five discrete Ir-bearing host phases were isolated in subsequent splits, having Ir masses equivalent to pure Ir spheres from about 0.8 to about 3.5 mm in diameter. Three of these are within a sufficiently reduced mass of powder to warrant searching for them using backscattered electron microscopy. In contrast, successively smaller splits of the Stevns Klint fish clay show no statistically significant deviation from the reported value of 32 +/- 2 ng/g Ir, suggesting a uniform Ir host-phase distribution. For the smallest split obtained thus far (100 +/- 40 ng/g Ir), a pure Ir sphere of equivalent Ir mass would be <0.05 min in diameter. (n.b. Although homogenizing and sieving of FC-1 to <75 min obviously obscured variations in stratigraphic distribution, it is unlikely to have affected the size-frequency distribution of Ir host phases.) We previously identified micrometer-scale Ir host phases by electron microscopy in melt-rock samples from two widely separated drill holes at the Chicxulub Basin, including a replicate split of Y6-NI9-R. One is an aggregate of subhedral Ir metal grains enclosed in silicate, in which no other Pt group elements (PGE) were detected. A second particle with twice the mass as the first, concentrated predominantly in a single grain, is associated with minor concentrations of Os, Ru, and Pt, and with adhering particles of corundum and perovskite. A third Ir-rich particle, with a greater apparent Os concentration, was identified before being lost as a result of charging under the electron beam. In addition to demonstrating the preservation of projectile components within the Chicxulub Crater, analogous phase associations in Ca- and Al-rich inclusions (CAI) from C2 and C3 chondrites suggest to us that these melt-rock Ir host phases are relics from a carbonaceous chondrite K/T boundary impactor Although the obviously low Ru/Ir ratios of the Chicxulub Ir host phases are qualitatively consistent with suggested PGE fractionation with distance during condensation in an ejecta cloud, it seems difficult to explain the accumulation of the about 3 x 10(exp 11) Ir atoms required to form a about 10(exp -10) g nugget of pure Ir metal within a jet of vaporized projectile expanding at 1-4 km/s, or to effectively exclude or remove commonly alloyed PGE and siderophile elements by fractionation processes resulting from condensation, oxidation, sulfidization, exsolution, or autometamorphism during cooling of the melt. We do not dismiss the importance of these processes entirely; on the contrary, other geochemical and mineralogical aspects of the melt rocks require them, and condensation from the expanding ejecta cloud appears to best explain the primary Ir host-phase distribution in the fish clay, as well as the high Ir concentrations associated with spinel-bearing spheroids at the K/T boundary in the Pacific Ocean . If the "relict" hypothesis is correct, micronuggets of other PGEs and alloys, not detected by our INAA screening, should also occur in the melt rocks. Possibly, the discrete host phases with lesser Ir masses are such alloys with subordinate Ir, rather than simply smaller, predominantly Ir-bearing particles. A CAI source for the relics would be consistent with either a comet or an asteroid K/T impact at Chicxulub. (Additional information contained in the original.)

Schuraytz, B. C.↗
DOE OSTI2021

Soil organic matter is principally root derived in an Ultisol under oak forest

To a large degree, the sources and stability of soil organic carbon remain poorly constrained. A clear understanding of links among the components of the soil C cycle is hampered by the complexity of the system as well as challenges associated with partitioning bulk soil C into meaningful fractions. A large accidental 14 CO 2 release at the Oak Ridge Reservation in Tennessee, USA provided a strong label pulse into adjacent, well-studied oak forests, resulting in highly elevated Δ 14 C values in leaf litter (~1000‰) and roots (~260–450‰). A four-year manipulative study was conducted to determine the relative contribution of litter versus roots to the bulk mineral soil C pool, as well as to free light, occluded light and heavy fractions. The heavy fraction was further split into fractions with densities of 1.7–2.4 g cm –3 and >2.4 g cm –3 to test the homogeneity of the mineral-associated fraction of C. Substantial concentrations of label were detected in all soil fractions within a year of the 14 CO 2 release, indicating rapid incorporation of newly fixed photosynthates in all fractions of soil organic C, regardless of differences in stability inferred by previous work. This rapid incorporation of label occurred only in treatments where roots were labeled, indicating that roots are the major source of inputs to mineral soil C stocks at these sites. Separation of the heavy fraction into subfractions of intermediate (1.7–2.4 g cm –3 ) and high (>2.4 g cm –3 ) density indicated that both subfractions incorporated label at similar rates, despite significant differences in degree of microbial processing. In general, the rate of label incorporation suggested a much faster turnover for all fractions than indicated by natural radiocarbon abundance values. This study suggests that within each soil fraction there are portions of slow-cycling and fast-cycling materials, and the determination of an average turnover time or mean age is dependent on experimental approach. The rapid incorporation of label into all fractions within a year regardless of inferred stability implies a high degree of heterogeneity in all fractions regardless of how finely the soils are partitioned. Further refinement of the nature and drivers of this heterogeneity could yield important insights into the soil C cycle.

58 GEOSCIENCES↗
DOE OSTI2020

Charge Transport in Zirconium-Based Metal–Organic Frameworks

Metal–organic frameworks (MOFs) are a class of crystalline porous materials characterized by inorganic nodes and multitopic organic linkers. Because of their molecular-scale porosity and periodic intraframework chemical functionality, MOFs are attractive scaffolds for supporting and/or organizing catalysts, photocatalysts, chemical-sensing elements, small enzymes, and numerous other functional-property-imparting, nanometer-scale objects. Notably, these objects can be installed after the synthesis of the MOF, eliminating the need for chemical and thermal compatibility of the objects with the synthesis milieu. Thus, postsynthetically functionalized MOFs can present three-dimensional arrays of high-density, yet well-separated, active sites. Depending on the application and corresponding morphological requirements, MOF materials can be prepared in thin-film form, pelletized form, isolated single-crystal form, polycrystalline powder form, mixed-matrix membrane form, or other forms. For certain applications, most obviously catalytic hydrolysis and electro- or photocatalytic water splitting, but also many others, an additional requirement is water stability. MOFs featuring hexa-zirconium(IV)-oxy nodes satisfy this requirement. For applications involving electrocatalysis, charge storage, photoelectrochemical energy conversion, and chemiresistive sensing, a further requirement is electrical conductivity, as embodied in electron or hole transport. As most MOFs, under most conditions, are electrically insulating, imparting controllable charge-transport behavior is both a chemically intriguing and chemically compelling challenge. Herein, we describe three strategies to render zirconium-based metal–organic frameworks (MOFs) tunably electrically conductive and, therefore, capable of transporting charge on the few nanometers (i.e., several molecular units) to few micrometers (i.e., typical dimensions for MOF microcrystallites) scale. The first strategy centers on redox-hopping between periodically arranged, chemically equivalent sites, essentially repetitive electron (or hole) self-exchange. Zirconium nodes are electrically insulating, but they can function as grafting sites for (a) redox-active inorganic clusters or (b) molecular redox couples. Alternatively, charge hopping based on linker redox properties can be exploited. Marcus’s theory of electron transfer has proven useful for understanding/predicting trends in redox-hopping based conductivity, most notably, in accounting for variations as great as 3000-fold depending on the direction of charge propagation through structurally anisotropic MOFs. In MOF environments, propagation of electronic charge via redox hopping is necessarily accompanied by movement of charge-compensating ions. Consequently, rates of redox hopping can depend on both the identity and concentration of ions permeating the MOF. In the context of electrocatalysis, an important goal is to transport electronic charge fast enough to match or exceed the inherent activity of MOF-based or MOF-immobilized catalysts. Bandlike electronic conductivity is the focus of an alternative strategy: one based on the introduction of molecular guests capable of forming donor–acceptor charge transfer complexes with the host framework. Theory again can be applied predictively to alter conductivity. A third strategy similarly emphasizes electronic conductivity, but it makes use of added bridges in the form of molecular oligomers or inorganic clusters that can then be linked to span the length of a MOF crystallite. For all strategies, retention of molecular-scale porosity is emphasized, as this property is key to many applications. Lastly, while our focus is on Zr-MOFs, the described approaches clearly are extendable to other MOF compositions, as has already been demonstrated, in part, in studies by others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1988

Sampling Mars: Analytical requirements and work to do in advance

Sending a mission to Mars to collect samples and return them to the Earth for analysis is without doubt one of the most exciting and important tasks for planetary science in the near future. Many scientifically important questions are associated with the knowledge of the composition and structure of Martian samples. Amongst the most exciting questions is the clarification of the SNC problem- to prove or disprove a possible Martian origin of these meteorites. Since SNC meteorites have been used to infer the chemistry of the planet Mars, and its evolution (including the accretion history), it would be important to know if the whole story is true. But before addressing possible scientific results, we have to deal with the analytical requirements, and with possible pre-return work. It is unlikely to expect that a possible Mars sample return mission will bring back anything close to the amount returned by the Apollo missions. It will be more like the amount returned by the Luna missions, or at least in that order of magnitude. This requires very careful sample selection, and very precise analytical techniques. These techniques should be able to use minimal sample sizes and on the other hand optimize the scientific output. The possibility to work with extremely small samples should not obstruct another problem: possible sampling errors. As we know from terrestrial geochemical studies, sampling procedures are quite complicated and elaborate to ensure avoiding sampling errors. The significance of analyzing a milligram or submilligram sized sample and putting that in relationship with the genesis of whole planetary crusts has to be viewed with care. This leaves a dilemma on one hand, to minimize the sample size as far as possible in order to have the possibility of returning as many different samples as possible, and on the other hand to take a sample large enough to be representative. Whole rock samples are very useful, but should not exceed the 20 to 50 g range, except in cases of extreme inhomogeneity, because for larger samples the information tends to become redundant. Soil samples should be in the 2 to 10 g range, permitting the splitting of the returned samples for studies in different laboratories with variety of techniques.

Koeberl, Christian↗
NASA NTRS2017

Meteoroid Bulk Density and Ceplecha Types

The determination of asteroid bulk density is an important aspect of Near Earth Object (NEO) characterization. A fraction of meteoroids originate from asteroids (including some NEOs), thus in lieu of mutual perturbations, satellites, or expensive spacecraft missions, a study of meteoroid bulk densities can potentially provide useful insights into the densities of NEOs and PHOs (Potentially Hazardous Objects). Meteoroid bulk density is still inherently difficult to measure, and is most often determined by modeling the ablation of the meteoroid. One approach towards determining a meteoroid density distribution entails using a more easily measured proxy for the densities, then calibrating the proxy with known densities from meteorite falls, ablation modelling, and other sources. An obvious proxy choice is the Ceplecha type, KB (Ceplecha, 1958), which is thought to indicate the strength of a meteoroid and often correlated to different bulk densities in literature. KB is calculated using the air density at the beginning height of the meteor, the initial velocity, and the zenith angle of the radiant; quantities more readily determined than meteoroid bulk density itself. Numerical values of K(sub B) are sorted into groups (A, B, C, etc.), which have been matched to meteorite falls or meteor showers with known composition such as the porous Draconids. An extensive survey was conducted to establish the strength of the relationship between bulk density and K(sub B), specifically looking at those that additionally determined K(sub B) for the meteors. In examining the modeling of high-resolution meteor data from Kikwaya et al. (2011), the correlation between K(sub B) and bulk density was not as strong as hoped. However, a distinct split by dynamical type was seen with Jovian Tisserand parameter (T(sub J)), with meteoroids from Halley Type comets (T(sub J) < 2) exhibiting much lower bulk densities than those originating from Jupiter Family comets and asteroids (T(sub J) > 2). Therefore, this work indicates that the dynamical classification of a meteoroid is a better indicator of the density than the strength proxy, a somewhat surprising result.

Blaauw, R. C.↗
DOE OSTI2022

MoO x S y /Ni 3 S 2 Microspheres on Ni Foam as Highly Efficient, Durable Electrocatalysts for Hydrogen Evolution Reaction

Hydrogen energy derived from water splitting is the cleanest renewable energy source, but it is also very challenging to achieve because the hydrogen evolution reaction (HER) requires highly efficient and low-cost electrocatalysts. Here, we have fabricated a novel hierarchical system of amorphous molybdenum oxy/sulfide microspheres with crystalline Ni 3 S 2 intergrown in situ on Ni foam (MoO x S y /Ni 3 S 2 /NF) as an outstanding electrocatalyst for HER. The MoO x S y /Ni 3 S 2 /NF demonstrates an ultra-low overpotential of 58 mV at a current density of 10 mA cm -2 and extremely durable stability (>200 h), suggesting superior performance comparable to that of Pt-C/NF under acidic conditions. The X-ray absorption fine structure (XAFS) determines the average valence state of Mo to be +(5 + δ), with a coordination motif by O and S. To explain such high HER activity, a [Mo 2 O 2 (S,O) 4 ] dimer-based periodic model structure with the average composition of [Mo 4 O 8 S 4 ] interfaced with the Ni 3 S 2 (101) surface is proposed. The interactions between the Ni of Ni 3 S 2 and bridging S/O of [Mo 4 O 8 S 4 ] result in an average formal Mo charge state between +5 and +6, and significant charge transfer from Ni 3 S 2 to [Mo 4 O 8 S 4 ] activates the Mo = O bonds. The calculated |ΔG H* | of less than 50 meV suggests that the double-bonded O is the most active site. This work points to the importance of oxy/sulfides with Mon+ (+5 < n < +6) as exceptional electrochemical catalysts for HER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2001

Impacts of ENSO on the South American Summer Monsoon During 1997-1999

Using the National Center for Environmental Prediction (NCEP) Reanalysis, and CPC Merged Analysis Product (CMAP) rainfall, we have compared and contrasted the anomalies of the South American Summer Monsoon (SASM) during two extreme years of 1997/98 (EI Nino) and 1998/99 (La Nina). The results are assessed against a "canonical" ENSO response (CER) pattern for the SASM obtained from empirical mode decomposition based on a previous period (1980-1995). Overall, the SASM anomalies compare well with CER, but with some important differences. Anomalies occurring in the warm phase of the 1997-98 El Nino are very significant and robust, while those occurring in 1998/99 La Nina, appear to be reversed from 1997/98, but are relatively weak and less well-defined. The most pronounced signal in DJF 1997/98 is the development of drought conditions in northern Brazil, excessive rainfall over northern Peru and Ecuador, and over Uruguay and southern Brazil. The tropical rainfall anomalies are associated with the eastward shift of the Walker circulation, which is represented by pronounced low-level anomalous westerlies over the equatorial eastern Pacific and easterlies over northern Brazil. The easterlies are deflected sharply southeastward by the steep topography of the Andes, enhancing the low-level jet (LLJ) along the eastern foothills of the Andes near 15-20 S. The LLJ penetrates deep into the extratropics, yielding rainfall anomalies further poleward compared to CER. During DJF 1997/98, the eastward expansion of the warm tropospheric temperature over the Nino-3 region causes anomalous geopotential height to develop in the upper troposphere above the Altiplano, leading to a strengthened Bolivian High. An upper-tropospheric jet anomaly maximum is found over the subtropical continent near 30 S, due to increasing meridional gradient of tropospheric temperature, as well as teleconnection patterns linking the South Pacific and the South Atlantic. Consistent with the CER, the South Pacific High is weakened, and the South Atlantic High is strengthened in DJF 1997/98. However, rather than appearing as a coherent large scale signal over the entire Atlantic as in CER, the South Atlantic High anomalies in DJF 1997/98 split into two separate high pressure centers; one located south of the Amazon basin, and another over the southeastern South Atlantic. The former is induced as a Rossby-wave response by ENSO-Induced sinking motion over nor-them and eastern Brazil, and the latter may be associated with extratropical teleconnection signals. Anomalous convection observed over equatorial western Africa may also have contributed to the different circulation response over the Atlantic in DFJ 1997/99 compared to the CER. Comparison of the evolution of the SASM anomalies in 1997-99 with their corresponding annual cycles, suggest that the anomalies are phase-locked to and represent either enhancement or reduction of the annual variations. Results suggest that, from a system perspective the SASM was strengthened during the 1997/98 El Nino and weakened, albeit to a lesser extent, during the 1998/99 La Nina.

Lau, K.-M.↗
DOE OSTI2024

Metal-facilitated, sustainable nitroarene hydrogenation under ambient conditions

Hydrogenation is a critical reaction in the chemical industry, yielding a range of important compounds such as fine chemicals, pharmachemicals and agrochemicals. However, conventional hydrogenation typically requires pressurized hydrogen, high temperatures and involves noble metal catalysts. Here, we proposed a two-step hydrogenation process, utilizing water as the hydrogen source for the industrially important reduction of nitroarenes to anilines. A metal or reduced metal oxide, which can be obtained from solar thermal or electrochemical reduction, acts as the active site for nitrobenzene adsorption, H 2 O dissociation and in-situ hydrogen generation. Among the 15 metal and reduced metal oxides investigated, Zn and Sn emerged as highly efficient catalysts for the reduction of a broad range of organic nitro compounds under mild conditions, with H 2 utilization efficiency 1-2 orders of magnitude above the state-of-the-art. The presented protocol provides extra dimensions for designing and optimizing conventional hydrogenation process with an alternative pathway. The reactive hydrogen atoms generated in-situ effectively overcome the barriers associated with hydrogen gas dissolution and its subsequent dissociation on the catalyst surface, thereby greatly enhancing the overall effectiveness for the hydrogenation reaction. This research potentially establishes a sustainable, generally applicable alternative to conventional hydrogenation methods, simultaneously presenting a viable solution for renewable energy storage.

25 ENERGY STORAGE↗
DOE OSTI2024

Time-dependent thermal degradation of lost circulation materials in geothermal systems

Treatment of lost circulation can represent anywhere from 5 to 25 % of the cost in drilling geothermal wells. The cost of the materials used for lost circulation treatment is less important than their effectiveness at reducing fluid losses. In geothermal systems, the high temperatures (>90 °C) are expected to degrade many commonly used lost circulation materials over time. This degradation could compromise different materials ability to mitigate fluid loss, creating more non-productive time as multiple treatments are needed, but may result in recovering desired permeability zones within the reservoir section over time. This research aimed to study how thermal degradation of eight different lost circulation materials affected their properties relevant to sealing loss zones in geothermal wells. Here, mass loss experiments were conducted with each material at temperatures of 90–250 °C for 1–42 days to measure the breakdown of the material at geothermal conditions, collecting gases during several experiments to determine the waste produced during degradation. Compaction experiments were conducted with the degraded materials to show how temperatures reduced the rigidity and increased packing of the materials. Viscosity tests were conducted to show the impact of different materials on drilling fluid rheology. Microscope observations were conducted to characterize the alterations to each material due to thermal degradation. Organic materials tend to degrade more than inorganic materials, with organics like microcellulose, cotton seed hulls and sawdust losing 30–50 % of their mass after 1 day of heating at 200 °C, while inorganics like magma fiber only lose ~5–10 % of its mass after one day of heating at 200 °C. Granular materials are the strongest when compacted despite any mass loss, while fibrous and flaky materials are fairly weak and breakdown easily under stress. The materials do not generally affect fluid rheology unless they have a viscosifying agent as part of the mixture. Microscopic analysis showed that more rigid materials like microcellulose and cedar fiber degrade in brittle manners with splitting and fracturing, while others like cotton seed hulls degrade in more ductile manners forming meshes or clumps of material. The thermal breakdown of lost circulation materials tested suggests that each material should also be classified by its degree of thermal degradability, as at certain temperatures the materials can lose the capability to bridge loss zones around the wellbore.

15 GEOTHERMAL ENERGY↗