Corporate acceleration of the renewable energy transition and implications for electric grids
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O'Shaughnessy, Eric (ORCID:0000000169280184)↗
SEARCH · Engineering Papers
Results for “transition pathways”
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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Sample preparation with sucrose cryoprotection dramatically alters Zn distribution in the rodent hippocampus, as revealed by elemental mapping
Transition metal ions (Fe, Mn, Cu, Zn) are essential for healthy brain function, but altered concentration, distribution, or chemical form of the metal ions has been implicated in numerous brain pathologies. Currently, it is not possible to image the cellular or sub-cellular distribution of metal ions in vivo and therefore, studying brain-metal homeostasis largely relies on ex vivo in situ elemental mapping. Sample preparation methods that accurately preserve the in vivo elemental distribution are essential if one wishes to translate the knowledge of elemental distributions measured ex vivo toward increased understanding of chemical and physiological pathways of brain disease. Furthermore, the choice of sample preparation is particularly important for metal ions that exist in a labile or mobile form, for which the in vivo distribution could be easily distorted by inappropriate sample preparation. One of the most widely studied brain structures, the hippocampus, contains a large pool of labile and mobile Zn. Herein, we describe how sucrose cryoprotection, the gold standard method of preparing tissues for immuno-histochemistry or immuno-fluorescence, which is also often used as a sample preparation method for elemental mapping studies, drastically alters hippocampal Zn distribution. Based on the results of this study, in combination with a comparison against the strong body of published literature that has used either rapid plunge freezing of brain tissue, or sucrose cryo-protection, we strongly urge investigators in the future to cease using sucrose cryoprotection as a method of sample preparation for elemental mapping, especially if Zn is an analyte of interest.
59 BASIC BIOLOGICAL SCIENCES↗
Closing the Loops on Solar Photovoltaics Modules: An Agent-Based Modeling Approach for the Study of Circular Economy Strategies
Solar photovoltaics (PV) installed capacity have grown exponentially since the early 2000s (average annual growth rate of 50%). With 4,700 GW projected installed capacity by 2050, the volume of PV panels waste is also expected to become substantial. Though renewables are a sine qua non to the establishment of a truly circular economy (CE), the issue arising from their end-of-life management needs to be resolved. The management of PV end-of-life also represent a singular opportunity to create value, from recovered valuable, rare or critical materials (e.g. silver, tellurium, indium). Moreover, the PV case illustrates some of the current barriers to CE; for instance, the need for a common definition of waste (PV are defined as e-waste in the European Union but as general waste in the United States) and potential loss of innovations' advantages (PV average efficiency has continuously grown the past 10 years). In this study, an agent-based modeling (ABM) approach is proposed to simulate PV end-of-life management in the United States. The model explores how the decisions of the various actors involved in handling PV waste affect the quantities of PV that are reused, recycled, or land-filled. In the model, manufacturers, residential, and nonresidential PV owners, installers, and recyclers are represented by agents while governmental policies and regulations are treated as exogenous variables. PV-market data are used to define agents' characteristics (e.g., installed PV capacities or producing costs). Agents' decision rules draw on the literature related to industrial symbiosis (IS) and peoples' waste behaviors as they appear as the most widely used model to implement CE principles at a meso level. Specifically, the concepts of mutual trust between IS actors and knowledge about the IS philosophy are yielded to define the agents' decision process. The primary outputs of the ABM are the costs and volume of waste associated with each end-of-life pathway. Preliminaries results indicate recycling of residential PV is affected by the cost, perceived difficulty of recycling behaviors, and social norms. Moreover, the type of network connecting agents and the initial recycling rate strongly influence results. The model also highlights the crucial role of recycling behavior adoption: in case of early failure of PV, recycled volumes increase by about 40%. This represents an additional 5.7 billion USD from potential recovered silver. Finally, although results for the PV case are presented here, the developed ABM aims at being a general tool for the study of CE strategies and the CE transition. Furthermore, steps of this research include extending the model to encompass circular economy strategies (e.g., design for recycling or lifetime extension) and validating its general architecture from various case studies.
14 SOLAR ENERGY↗
Lattice-Oxygen-Driven Selective Oxidation Strategy for Stable Argyrodite Solid-State Lithium Metal Batteries
All-solid-state lithium metal batteries (ASSLMBs) with Li6PS5Cl argyrodite electrolytes and high-voltage LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes offer high energy density but suffer from rapid capacity fading due to the layered-to-rock-salt transition of NMC811 and structural degradation of Li6PS5Cl from parasitic interfacial reactions. Here, we demonstrate a catholyte engineering strategy using a Li2S scavenging additive to suppress interfacial reactivity and preserve the structural and electrochemical stability of both NMC811 and Li6PS5Cl. Incorporating 0.10 wt.% Li2S enables exceptional cycling stability, achieving 76% capacity retention after 550 cycles at C/10 and 88% retention after 800 cycles at C/3 at 60 degrees C, compared with rapid failure in pristine cells. Spectroscopic, electrochemical, and morphological analyses confirm that Li2S maintains electrode integrity by sustaining particle contact and suppressing phase decomposition. This work elucidates interfacial degradation pathways in NMC811/argyrodite systems and introduces a low-cost, scalable strategy to stabilize nickel-rich oxide cathodes in ASSLMBs, advancing their practical viability.
25 ENERGY STORAGE↗
Revealing the two-dimensional electronic structure and anisotropic superconductivity in a natural van der Waals superlattice (PbSe) 1.14 NbSe 2
Van der Waals superlattices are important for tailoring the electronic structures and properties of layered materials. Here we report the superconducting properties and electronic structure of a natural van der Waals superlattice (PbSe) 1.14 NbSe 2 . Anisotropic superconductivity with a transition temperature T c = 5.6 ± 0.1 K, which is higher than monolayer NbSe 2 , is revealed by transport measurements on high-quality samples. Angle-resolved photoemission spectroscopy (ARPES) measurements reveal the two-dimensional electronic structure and a charge transfer of 0.43 electrons per NbSe 2 unit cell from the blocking PbSe layer. In addition, polarization-dependent ARPES measurements reveal a significant circular dichroism with opposite contrast at K and K' valleys, suggesting a significant spin-orbital coupling and distinct orbital angular momentum. In conclusion, our work suggests natural van der Waals superlattice as an effective pathway for achieving intriguing properties distinct from both the bulk and monolayer samples.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Cation reordering instead of phase transitions: Origins and implications of contrasting lithiation mechanisms in 1D ζ- and 2D α-V 2 O 5
Substantial improvements in cycle life, rate performance, accessible voltage, and reversible capacity are required to realize the promise of Li-ion batteries in full measure. Here, we have examined insertion electrodes of the same composition (V 2 O 5 ) prepared according to the same electrode specifications and comprising particles with similar dimensions and geometries that differ only in terms of their atomic connectivity and crystal structure, specifically two-dimensional (2D) layered α-V 2 O 5 that crystallizes in an orthorhombic space group and one-dimensional (1D) tunnel-structured ζ-V 2 O 5 crystallized in a monoclinic space group. By using particles of similar dimensions, we have disentangled the role of specific structural motifs and atomistic diffusion pathways in affecting electrochemical performance by mapping the dynamical evolution of lithiation-induced structural modifications using ex situ scanning transmission X-ray microscopy, operando synchrotron X-ray diffraction measurements, and phase-field modeling. We find the operation of sharply divergent mechanisms to accommodate increasing concentrations of Li-ions: a series of distortive phase transformations that result in puckering and expansion of interlayer spacing in layered α-V 2 O 5 , as compared with cation reordering along interstitial sites in tunnel-structured ζ-V 2 O 5 . By alleviating distortive phase transformations, the ζ-V 2 O 5 cathode shows reduced voltage hysteresis, increased Li-ion diffusivity, alleviation of stress gradients, and improved capacity retention. The findings demonstrate that alternative lithiation mechanisms can be accessed in metastable compounds by dint of their reconfigured atomic connectivity and can unlock substantially improved electrochemical performance not accessible in the thermodynamically stable phase.
25 ENERGY STORAGE↗
Metal Site Substitution and Role of the Dimer on Symmetry Breaking in FePS 3 and CrPS 4 under Pressure
We combine infrared absorption, Raman scattering, and diamond anvil cell techniques to explore the properties of FePS 3 and CrPS 4 under pressure, comparing our findings with a symmetry analysis, lattice dynamics calculations, and an examination of the energy landscape. Although these complex chalcogenides are considered to be members of the same family of materials, they display remarkably different phase progressions on account of the metal center orbital filling, character of the P–P linkage, layer corrugation, and differing size of the van der Waals gap. Here, we discuss the space group progressions, structure–property relations, and development of pressure-induced metallicity in terms of the competition between local and long-range symmetry transformations and structural distortion pathways. These findings place the properties of FePS 3 and CrPS 4 on a firm foundation for work under strain control and in the single layer limit.
36 MATERIALS SCIENCE↗
Superconductivity in the Parent Infinite-Layer Nickelate NdNiO 2
We report evidence for superconductivity with onset temperatures up to 11 K in thin films of the infinite-layer nickelate parent compound NdNiO 2 . A combination of oxide molecular beam epitaxy and atomic hydrogen reduction yields samples with high crystallinity and low residual resistivities, a substantial fraction of which exhibit superconducting transitions. We survey a large series of samples with a variety of techniques, including electrical transport, scanning transmission electron microscopy, x-ray absorption spectroscopy, and resonant inelastic x-ray scattering, to investigate the possible origins of superconductivity. We propose that superconductivity could be intrinsic to the undoped infinite-layer nickelates but suppressed by disorder due to a possibly sign-changing order parameter, a finding which would necessitate a reconsideration of the nickelate phase diagram. Another possible hypothesis is that the parent materials can be hole doped from randomly dispersed apical oxygen atoms, which would suggest an alternative pathway for achieving superconductivity. Published by the American Physical Society 2025
36 MATERIALS SCIENCE↗
Equally parsimonious pathways through an RNA sequence space are not equally likely
An experimental system for determining the potential ability of sequences resembling 5S ribosomal RNA (rRNA) to perform as functional 5S rRNAs in vivo in the Escherichia coli cellular environment was devised previously. Presumably, the only 5S rRNA sequences that would have been fixed by ancestral populations are ones that were functionally valid, and hence the actual historical paths taken through RNA sequence space during 5S rRNA evolution would have most likely utilized valid sequences. Herein, we examine the potential validity of all sequence intermediates along alternative equally parsimonious trajectories through RNA sequence space which connect two pairs of sequences that had previously been shown to behave as valid 5S rRNAs in E. coli. The first trajectory requires a total of four changes. The 14 sequence intermediates provide 24 apparently equally parsimonious paths by which the transition could occur. The second trajectory involves three changes, six intermediate sequences, and six potentially equally parsimonious paths. In total, only eight of the 20 sequence intermediates were found to be clearly invalid. As a consequence of the position of these invalid intermediates in the sequence space, seven of the 30 possible paths consisted of exclusively valid sequences. In several cases, the apparent validity/invalidity of the intermediate sequences could not be anticipated on the basis of current knowledge of the 5S rRNA structure. This suggests that the interdependencies in RNA sequence space may be more complex than currently appreciated. If ancestral sequences predicted by parsimony are to be regarded as actual historical sequences, then the present results would suggest that they should also satisfy a validity requirement and that, in at least limited cases, this conjecture can be tested experimentally.
NASA Discipline Exobiology↗
Kinetic conversion of CO to CH4 in the Solar System
Some of the most interesting chemistry in the Solar System involves changes in the oxidation state of the simple carbon species. The chemical pathways for the conversion of CH4 to CO and CO2 are for the most part known. The reverse process, the reduction of CO to CH4, is, however, poorly understood. This is surprising in view of the importance of the reduction process in the chemistry of the Solar System. Recently we investigated the chemical kinetics of a hitherto unsuspected reaction. It is argued that the formation of the methoxy radical (CH3O) from H+H2CO may play an essential role in the reduction of CO to CH4. The rate coefficient for this reaction has been estimated using the approximate theory of J. Troe and transition state theory. We will discuss the implications of this reaction for the chemistry of CO on Jupiter, in the solar nebula, for interpreting the laboratory experiments of A. Bar-Nun and A. Shaviv and A. Bar-Nun and S. Chang, and for organic synthesis in the prebiotic terrestrial atmosphere. The possible relation of CO reduction in the solar nebula and polyoxymethylene observed in comet Halley will be discussed.
Yung, Y. L.↗
A genetic technique for planning a control sequence to navigate the state space with a quasi-minimum-cost output trajectory for a non-linear multi-dimnensional system
There are many multi-stage optimization problems that are not easily solved through any known direct method when the stages are coupled. For instance, we have investigated the problem of planning a vehicle's control sequence to negotiate obstacles and reach a goal in minimum time. The vehicle has a known mass, and the controlling forces have finite limits. We have developed a technique that finds admissible control trajectories which tend to minimize the vehicle's transit time through the obstacle field. The immediate applications is that of a space robot which must rapidly traverse around 2-or-3 dimensional structures via application of a rotating thruster or non-rotating on-off for such vehicles is located at the Marshall Space Flight Center in Huntsville Alabama. However, it appears that the development method is applicable to a general set of optimization problems in which the cost function and the multi-dimensional multi-state system can be any nonlinear functions, which are continuous in the operating regions. Other applications included the planning of optimal navigation pathways through a transversability graph; the planning of control input for under-water maneuvering vehicles which have complex control state-space relationships; the planning of control sequences for milling and manufacturing robots; the planning of control and trajectories for automated delivery vehicles; and the optimization and athletic training in slalom sports.
Hein, C.↗
Conformer-Dependent Chemistry: Experimental Product Branching of the Vinyl Alcohol + OH + O 2 Reaction
The concentration of formic acid in Earth's tropo-sphere is underestimated by detailed chemical models compared to field observations. Phototautomerization of acetaldehyde to its less stable tautomer vinyl alcohol, followed by the OH-initiated oxidation of vinyl alcohol, has been proposed as a missing source of formic acid that improves the agreement between models and field measurements. Theoretical investigations of the OH + vinyl alcohol reaction in excess O 2 conclude that OH addition to the alpha carbon of vinyl alcohol produces formaldehyde + formic acid + OH, whereas OH addition to the β site leads to glycoaldehyde + HO 2 . Furthermore, these studies predict that the conformeric structure of vinyl alcohol controls the reaction pathway, with the anti-conformer of vinyl alcohol promoting α OH addition, whereas the syn-conformer promotes β addition. However, the two theoretical studies reach different conclusions regarding which set of products dominate. We studied this reaction using time-resolved multiplexed photoionization mass spectrometry to quantify the product branching fractions. Our results, supported by a detailed kinetic model, conclude that the glycoaldehyde product channel (arising mostly from syn-vinyl alcohol) dominates over formic acid production with a 3.6:1.0 branching ratio. Additionally, this result supports the conclusion of Lei et al. that conformer-dependent hydrogen bonding at the transition state for OH-addition controls the reaction outcome. As a result, tropospheric oxidation of vinyl alcohol creates less formic acid than recently thought, increasing again the discrepancy between models and field observations of Earth's formic acid budget.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Influence of Linker Identity on the Photochemistry of Uranyl-Organic Frameworks
While uranyl-based metal–organic frameworks (MOFs) boast impressive photocatalytic abilities, significant questions remain regarding their excitation pathways and methods to fine-tune their performance due to the lack of information regarding heterogeneous uranyl catalysis. Herein, we investigated how linker identity and photoexcitation impact uranyl photocatalysis when the uranyl coordination environment remains constant. Toward this end, we prepared three uranyl-based MOFs (NU-1301, NU-1307, and ZnTCPP-U2) and then examined the structural and photochemical properties of each through X-ray diffraction, X-ray absorption, and photoluminescence. We then correlated our observations to the photocatalytic performance for fluorination of cyclooctane. The excitation profile from NU-1301 and NU-1307 exhibited spin-forbidden linker transitions and uranyl vibronic progressions, with uranyl excitation and emission being most dominant in NU-1301. Consequently, NU-1301 was a more active photocatalyst than NU-1307. In contrast, the excitation profile from ZnTCPP-U2 contained transitions associated with the porphyrin linker exclusively. Photocatalytic activity from ZnTCPP-U2 significantly underperformed in comparison to that of the other two MOFs. Furthermore, these data suggest that linkers’ photophysical properties can be used to predict the photocatalytic behavior of uranyl-containing MOFs.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Bond Selective Photochemistry at Metal Nanoparticle Surfaces: CO Desorption from Pt and Pd
The use of visible photon fluxes to influence catalytic reactions on metal nanoparticle surfaces has attracted attention based on observations of reaction mechanisms and selectivity not observed under equilibrium heating. These observations suggest that photon fluxes can selectively impact the rates of certain elementary steps, creating nonequilibrium energy distributions among various reaction pathways. However, quantitative studies validating these hypotheses on metal nanoparticle surfaces are lacking. Here, we examine the influence of continuous wave visible photon fluxes on the CO desorption rates from 1 to 2 nm diameter Pt and Pd nanoparticle surfaces supported on γ-Al 2 O 3 . Temperature-programmed desorption measurements quantified via diffuse reflectance infrared Fourier transform spectroscopy demonstrate that visible photon fluxes significantly enhanced the rate of CO desorption from Pt nanoparticles in a wavelength-dependent manner. 440 nm photons most efficiently promoted CO desorption from Pt nanoparticle surfaces, aligning with the excitation energy for the interfacial electronic transition within the Pt–CO bond. Conversely, visible photon fluxes had no measurable influence on CO desorption rates from Pd nanoparticle surfaces after accounting for photon-induced heating. Density functional theory calculations demonstrate that the Pt–CO bond exhibits a narrower LUMO resonance, stronger coupling between the photoexcitation and forces induced on the metal–C bond, and vibrational energy dissipation that more effectively couples to desorption as compared to Pd–CO. These results demonstrate the specificity photons provide in facilitating chemical reactions on metal nanoparticle surfaces and substantiate the idea that photon fluxes can steer processes and outcomes of catalytic reactions in ways not achievable by equilibrium heating.
desorption↗
Synthesis and Exploratory Catalysis of 3d Metals: Atom and Group-Transfer Reactions and the Activation and Functionalization of Small Molecules Including Greenhouse Gases
Determining ways to convert natural gas, with zero emissions, and to more value-added materials such as olefins is one of the main goals in my research group. Over this funding period, we explored the chemistry of early-transition metals with metal-nitrogen multiple bonds, specifically titanium and zirconium nitrides, and explored their redox properties, basicity and reactivity with small molecules including greenhouses gases such as carbon dioxide. Some of these work serve as inspiration for the chemistry of important materials such as uranium nitride along with its unprecedented basicity and ability to activate C-H bonds. Using robust chelating templates we also examined rare examples of trivalent group 4 transition metal ions, and studied these spectroscopically. Using early transition metal ions we also explored synthetic routes to new phosphide based products using the phosphaethynolate salt. In addition, we also explored the chemistry of ferrous systems, and redox active ligand that can allow us to reversibly break and make C-S as well as N-N bonds, activate dinitrogen forming unusual MNNM topologies. Our final component describes how we activate methane and dehydrocouple if with a carbene source to form ethylene. Using this information, we also discovered a simple to make iridium catalyst that activate and functionalize methane with 9:1 selectivity for mono-functionalization. We have established a pathway that leads to poisoning of the catalyst and have found optimal conditions for higher selectivity and with over 170 Turnovers.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Pulsed Light Synthesis of High Entropy Nanocatalysts with Enhanced Catalytic Activity and Prolonged Stability for Oxygen Evolution Reaction
The ability to synthesize compositionally complex nanostructures rapidly is a key to high-throughput functional materials discovery. In addition to being time-consuming, a majority of conventional materials synthesis processes closely follow thermodynamics equilibria, which limit the discovery of new classes of metastable phases such as high entropy oxides (HEO). Herein, a photonic flash synthesis of HEO nanoparticles at timescales of milliseconds is demonstrated. By leveraging the abrupt heating and cooling cycles induced by a high-power-density xenon pulsed light, mixed transition metal salt precursors undergo rapid chemical transformations. Hence, nanoparticles form within milliseconds with a strong affinity to bind to the carbon substrate. Oxygen evolution reaction (OER) activity measurements of the synthesized nanoparticles demonstrate two orders of magnitude prolonged stability at high current densities, without noticeable decay in performance, compared to commercial IrO 2 catalyst. This superior catalytic activity originates from the synergistic effect of different alloying elements mixed at a high entropic state. It is found that Cr addition influences surface activity the most by promoting higher oxidation states, favoring optimal interaction with OER intermediates. The proposed high-throughput method opens new pathways toward developing next-generation functional materials for various electronics, sensing, and environmental applications, in addition to renewable energy conversion.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Funneled Depolymerization of Ionic Liquid-Based Biorefinery “Heterogeneous” Lignin into Guaiacols over Reusable Palladium Catalyst
The efficient utilization of lignin, the direct source of renewable aromatics, into value-added renewable chemicals is an important step towards sustainable biorefinery practices. Nevertheless, owing to the random heterogeneous structure and limited solubility, lignin utilization has been primarily limited to burning for energy. The catalytic depolymerization of lignin has been proposed and demonstrated as a viable route to sustainable biorefinery, however, low yields and poor selectivity of products, high char formation, and limited to no recycling of transition-metal-based catalyst involved in lignin depolymerization demands attention to enable practical-scale lignocellulosic biorefineries. In this study, we demonstrate the catalytic depolymerization of ionic liquid-based biorefinery poplar lignin into guaiacols over a reusable zirconium phosphate supported palladium catalyst. The essence of the study lies in the high conversion (>80 %), minimum char formation (7–16 %), high yields of guaiacols (up to 200 mg / g of lignin), and catalyst reusability. In conclusion, both solid residue, liquid stream, and gaseous products were thoroughly characterized using ICP-OES, PXRD, CHN analysis, GC-MS, GPC, and 2D NMR to understand the hydrogenolysis pathway.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Nonparametric extensions of nuclear equations of state: Probing the breakdown scale of relativistic mean-field theory
Phenomenological calculations of the properties of dense matter, such as relativistic mean-field theories, represent a pathway to predicting the microscopic and macroscopic properties of neutron stars. However, such theories do not generically have well-controlled uncertainties and may break down within neutron stars. To faithfully represent the uncertainty in this breakdown scale, we develop a hybrid representation of the dense-matter equation of state, which assumes the form of a relativistic mean-field theory at low densities, while remaining agnostic to any nuclear theory at high densities. To achieve this, we use a nonparametric equation of state model to incorporate the correlations of the underlying relativistic mean-field theory equation of state at low pressures and transition to more flexible correlations above some chosen pressure scale. We perform astrophysical inference under various choices of the transition pressure between the theory-informed and theory-agnostic models. Here, we further study whether the chosen relativistic mean-field theory breaks down above some particular pressure and find no such evidence. Using simulated data for future astrophysical observations at about two-to-three times the precision of current constraints, we show that our method can identify the breakdown pressure associated with a potential strong phase transition.
Equations of state of nuclear matter↗