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At least 325 records · Page 18

Energy-efficient carbon capture from industrial point sources via commercially available green solvent and hollow fiber membrane contactors

Solvent-based absorption systems have emerged in the carbon capture space due to their high absorption capacities, reusability, and favorable energy requirements. Using diethyl sebacate as a solvent for pre- and post-combustion carbon capture has advantages over other solvents, including high hydrophobicity, low viscosity, low vapor pressure, high CO 2 solubility, high CO 2 selectivity, and being commercially available in large quantities. Despite these advantageous properties, the use of diethyl sebacate as a solvent for post-combustion carbon capture has not been studied in detail. To examine the capability of diethyl sebacate, a scalable, energy-efficient, hollow fiber membrane (microporous polypropylene and polyvinylidene fluoride) contactor (HFMC)-based process with low-cost and high surface area is investigated. A purity of 95.3 % CO 2 with 46 % recovery in one absorption stage was achieved, with a permeate flux over one magnitude greater than using a deep eutectic solvent in the same system. Technoeconomic analysis determined a ∼ 0.8 GJ per ton of CO 2 at a processing cost of ∼$93 per ton of CO 2 . Results from this work underscore the potential for utilizing green solvents in HFMC-based separation processes for effective carbon capture and provide a pathway towards practical deployment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inverse bremsstrahlung absorption rate for super-Gaussian electron distribution functions including plasma screening

Here we provide analytic expressions for the effective Coulomb logarithm for inverse bremsstrahlung absorption which predict significant corrections to the Langdon effect and overall absorption rate compared to previous estimates. The calculation of the collisional absorption rate of laser energy in a plasma by the inverse bremsstrahlung mechanism usually makes the approximation of a constant Coulomb logarithm. We dispense with this approximation and instead take into account the velocity dependence of the Coulomb logarithm, leading to a more accurate expression for the absorption rate valid in both classical and quantum conditions. In contrast to previous work, the laser intensity enters into the Coulomb logarithm. In most laser-plasma interactions the electron distribution function is super-Gaussian [Langdon, Phys. Rev. Lett. 44, 575 (1980)], and we find the absorption rate under these conditions is increased by as much as ≈ 30% compared to previous estimates at low density. In many cases of interest the correction to Langdon's predicted reduction in absorption is large; for example at Z = 6 and Te = 400 eV the Langdon prediction for the absorption is in error by a factor of ≈ 2. However, we also account for the additional effect of plasma screening, which predicts a reduction in absorption by a similar amount (up to ≈ 30%). These two effects compete to determine the overall absorption, which may be increased or decreased, depending on the conditions. The corrections can be incorporated into radiation-hydrodynamics simulation codes by replacing the familiar Coulomb logarithm with an analytic expression which depends on the super-Gaussian order “M” and the screening length.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

CdZnTeSe: Recent advances for radiation detector applications

The quest for cost-effective, high performing room temperature semiconductor detector (RTSD) materials for high energy gamma rays has been continuing for more than three decades. The requirements for RTSD materials, however, are more stringent as compared to other applications unrelated to detection of X- and gamma-rays, mainly due to the requirement of thick detectors for sufficient absorption of high-energy electromagnetic radiation and excellent charge-transport properties. The II-VI compound CdZnTe (CZT) with the composition of 10 atomic % Zn (Cd0.9Zn0.1Te) has been the material of choice over the past several years, and it has dominated the commercial market for RTSD materials and detectors. Despite its commercial success as a room temperature radiation detection material, CZT suffers from a lack of compositional homogeneity on both a micro- and macro-scale and the presence of high concentrations of sub-grain boundary (dislocation walls) networks and secondary phases (Te-rich inclusions). This chapter focuses on the presence of performance-limiting defects in CZT that hinder the yield and elevate the cost of high-quality detectors. The presence of such performance-limiting defects has restricted widespread deployment of CZT for a variety of potential applications, particularly for uses of relatively large detectors where the demands on material perfection are significantly greater. In the recent past, replacing some of the tellurium with selenium in the CZT matrix was found to be very effective in drastically reducing the Te-rich secondary phases and dislocation networks, plus

Roy, Utpal N.↗

Quantization effects in semiconductor nanostructures and singlet fission in molecular chromophores for photovoltaics and solar fuels

Hot carriers in semiconductors are electrons and/or holes that have energies greater than carriers that reside at the top and bottom of the conduction and valence bands, respectively; the latter carriers are in equilibrium with the lattice and have a temperature equal to the lattice (ambient) temperature. Hot carriers are created in semiconductors upon the absorption of photons with energies greater than the bandgap. The excess energy above the bandgap energy is in the form of kinetic energy. The hot carriers can cool to the lattice temperature via electron–phonon scattering and establish separate Boltzmann distributions for electrons and holes at the band edges. Thus, upon cooling, the excess kinetic energy of the hot carriers is transformed into heat and is unavailable to be converted into electrical or chemical free energy in a solar photon-converting cell. This hot-carrier cooling process significantly limits the maximum possible power conversion efficiency (PCE) of the free energy of solar photons into electrical free energy or chemical free energy in chemical bonds of fuels. However, if hot-carrier cooling can be slowed such that the hot carriers can be extracted before cooling to create higher photovoltages, or utilized to create additional electron-hole pairs through carrier multiplication, then beneficial use can be made of the excess energy of hot carriers and the maximum thermodynamic PCE can be dramatically increased. Quantization effects in semiconductor nanostructures, unique properties of some bulk semiconductors, and exciton multiplication in both semiconductors and molecular chromophores that undergo singlet fission have shown a path forward for potential dramatic increases in the PCEs of solar photons into electricity and solar fuels. The status, history, and future promise of the science and technology of these future approaches for different types of photovoltaic cells and cells for solar fuels will be discussed.

14 SOLAR ENERGY↗

Resonance Raman Study of Shell Morphology in InP/ZnSe/ZnS Core/Shell/Shell Nanocrystals

Resonance Raman spectra and absolute cross sections of InP/ZnSe/ZnS core/shell/shell nanocrystals have been obtained at excitation wavelengths of 501.7, 457.9, and 410 nm. Eight different structures having nearly the same lowest excitonic absorption wavelength but significantly different stoichiometries are compared. The Raman spectra show phonon features attributable to both the InP core and the ZnSe shell. The largest differences among the structures are seen in the ZnSe phonon region by using excitation at 457.9 nm, on the low-energy edge of the absorption features having significant contributions from the ZnSe shell. Here, structures that are nearly stoichiometric (In:P ratio ≈1.0) show a sharp, strongly polarized peak near the bulk ZnSe phonon frequency (~250 cm –1 ) and a weak lower-frequency shoulder with a higher depolarization ratio. Structures having excess indium show a stronger low-frequency shoulder near 225 cm –1 and lower integrated Raman intensities throughout the ZnSe phonon region. These changes are attributed to the presence of indium atoms in the ZnSe shell. Furthermore, these results support a previous assignment of a slow rise component in the time-resolved photoluminescence spectra of nonstoichiometric structures to transient trapping of holes at indium defects in the shell.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Interligand Coupling Drives Fast Triplet Energy Transfer Routes in PbS/Tetracene Quantum Dot Hybrids

The binding of photoactive organic ligands to inorganic quantum dots (QDs) creates a versatile hybrid architecture that allows access to photophysical processes such as efficient triplet exciton generation with near-infrared radiation. Here we report the subnanosecond generation of a hybrid triplet state with mixed ligand-QD character by replacing native oleate ligands on small PbS QDs with 5,12-tetracenepropiolic acid, a bifunctional ligand with two carboxylic acids that tends to lie face-on with the QD surface at low loadings. The face-on geometry engenders a regime of strong electronic coupling that is evident in steady-state absorption and hastens triplet energy flow by several orders of magnitude compared with more typical tetracene-based ligands exhibiting weak coupling. We further determined via Fourier transform infrared (FTIR) and supported by density functional theory (DFT)-based geometry optimizations that high ligand loading causes a shift in QD-ligand mutual disposition toward an edge-on geometry that instigates the formation of intermolecular excited states characterized by triplet excimer-like features in photoluminescence and transient absorption. Our results demonstrate the ability to control strongly coupled ligand-QD systems toward ultrafast generation of photophysically relevant species such as triplets that are valuable for photon upconversion and catalysis.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Energy dissipation efficiency in the CP43 assembly intermediate complex of photosystem II

Photosystem II in oxygenic organisms is a large membrane bound rapidly turning over pigment protein complex. During its biogenesis, multiple assembly intermediates are formed, including the CP43-preassembly complex (pCP43). Here, to understand the energy transfer dynamics in pCP43, we first engineered a His-tagged version of the CP43 in a CP47-less strain of the cyanobacterium Synechocystis 6803. Isolated pCP43 from this engineered strain was subjected to advanced spectroscopic analysis to evaluate its excitation energy dissipation characteristics. These included measurements of steady-state absorption and fluorescence emission spectra for which correlation was tested with Stepanov relation. Comparison of fluorescence excitation and absorptance spectra determined that efficiency of energy transfer from β-carotene to chlorophyll a is 39 %. Time-resolved fluorescence images of pCP43-bound Chl a were recorded on streak camera, and fluorescence decay dynamics were evaluated with global fitting. These demonstrated that the decay kinetics strongly depends on temperature and buffer used to disperse the protein sample and fluorescence decay lifetime was estimated in 3.2–5.7 ns time range, depending on conditions. The pCP43 complex was also investigated with femtosecond and nanosecond time-resolved absorption spectroscopy upon excitation of Chl a and β-carotene to reveal pathways of singlet excitation relaxation/decay, Chl a triplet dynamics and Chl a → β-carotene triplet state sensitization process. The latter demonstrated that Chl a triplet in the pCP43 complex is not efficiently quenched by carotenoids. Finally, detailed kinetic analysis of the rise of the population of β-carotene triplets determined that the time constant of the carotenoid triplet sensitization is 40 ns.

59 BASIC BIOLOGICAL SCIENCES↗

Probing Mg Intercalation in the Tetragonal Tungsten Bronze Framework V 4 Nb 18 O 55

While commercial Li-ion batteries offer the highest energy densities of current rechargeable battery technologies, their energy storage limit has almost been achieved. Therefore, there is considerable interest in Mg batteries, which could offer increased energy densities in comparison to Li-ion batteries if a high-voltage electrode material, such as a transition-metal oxide, can be developed. However, there are currently very few oxide materials which have demonstrated reversible and efficient Mg 2+ insertion and extraction at high voltages; this is thought to be due to poor Mg 2+ diffusion kinetics within the oxide structural framework. Here, in this paper, the authors provide conclusive evidence of electrochemical insertion of Mg 2+ into the tetragonal tungsten bronze V 4 Nb 18 O 55 , with a maximum reversible electrochemical capacity of 75 mA h g –1 , which corresponds to a magnesiated composition of Mg 4 V 4 Nb 18 O 55 . Experimental electrochemical magnesiation/demagnesiation revealed a large voltage hysteresis with charge/discharge (1.12 V vs Mg/Mg 2+ ); when magnesiation is limited to a composition of Mg 2 V 4 Nb 18 O 55 , this hysteresis can be reduced to only 0.5 V. Hybrid-exchange density functional theory (DFT) calculations suggest that a limited number of Mg sites are accessible via low-energy diffusion pathways, but that larger kinetic barriers need to be overcome to access the entire structure. The reversible Mg 2+ intercalation involved concurrent V and Nb redox activity and changes in crystal structure, as confirmed by an array of complementary methods, including powder X-ray diffraction, X-ray absorption spectroscopy, and energy-dispersive X-ray spectroscopy. Consequently, it can be concluded that the tetragonal tungsten bronzes show promise as intercalation electrode materials for Mg batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrafast Charge Transfer Dynamics at the Origin of Photoconductivity in Doped Organic Solids

In spite of their growing importance for optoelectronic devices, the fundamental properties and photophysics of molecularly doped organic solids remain poorly understood. Such doping typically leads to a small fraction of free conductive charges, with most electronic carriers remaining Coulombically bound to the ionized dopant. Recently, we have reported photocurrent for devices containing vacuum-deposited TAPC (1,1-bis(4-bis(4- methylphenyl)aminophenyl)cyclohexane) doped with MoO 3 , showing that photoexcitation of charged TAPC molecules increases the concentration of free holes that contribute to conduction. Here, we elucidate the excited-state dynamics of such doped TAPC films to unravel the key mechanisms responsible for this effect. We demonstrate that excitation of different electronic transitions in charged and neutral TAPC molecules allows bound holes to overcome the Coulombic attraction to their MoO 3 counterions, resulting in an enhanced yield of long-lived free carriers. This is caused by ultrafast back-and-forth shuffling of charges and excitation energy between adjacent cations and neutral molecules, competing with relatively slow nonradiative decay from higher excited states of TAPC •+ . The light-induced generation of conductive carriers requires the coexistence of cationic and neutral TAPC, a favorable energy level alignment, and intermolecular interactions in the solid state.

36 MATERIALS SCIENCE↗

Domain Separated Density Functional Theory for Reaction Energy Barriers and Optical Excitations

We recently proposed Domain Separated Density Functional Theory (DS-DFT), a framework that allows for the combination of different levels of theory for the computation of the electronic structure of molecules. Here, this work discusses the application of DS-DFT to the computation of transition-state energy barriers and optical absorption spectra. We considered several hydrogen abstraction reactions and optical spectra of molecule/metal cluster systems, including the absorption of individual species such as carbon monoxide, methane, and molecular hydrogen to a Li6 cluster. We present and discuss two domain-separated methods: i), the screened-density approximation (SDA), and, ii), linearly weighted exchange (LWE). We find that SDA, which is applied as a hybridization based on atomic domains, could be useful to computing energy barriers, whereas LWE is suited for the analysis of electronic properties such as ground-state gaps, excitation energies, and oscillator strengths.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interpretation of Ir L-edge isotropic x-ray absorption spectra across the pressure-induced dimerization transition in hyper-honeycomb beta-Li2IrO3

The extended nature of atomic 5d orbitals, together with a relatively short ~ 3 °A Ir-Ir distance across edge-shared octahedra in honeycomb iridate lattices, leads to a tendency to disrupt the local, spin-orbit entangled jeff = 1 2 moments of Ir4+ ions in favor of dimerization and formation of molecular orbitals, especially upon lattice compression. The sensitivity of Ir L-edge spectroscopy to both spin-orbit entanglement in jeff states and quenching of orbital degrees of freedom in dimerized states, results in a peculiar evolution of x-ray absorption spectra across dimerization transitions including energy shifts in opposite direction for L3 and L2 leading absorption edges, and substantial changes in their isotropic branching ratio. We present a theoretical description of the evolution of 5d electronic states, and related x-ray absorption spectra, in going from the single ion to the dimerized limit. The calculations reproduce the experimental results for hyper-honeycomb β-Li2IrO3[1, 2] and shed light into the weakening of the coupling between spin and orbital degrees of freedom as the strength of dimerization increases. The results provide a basis for interpretation of L-edge xray absorption spectra in 5d systems where competition between formation of local jeff states and molecular orbitals is at play.

van Veenendaal, Michel↗

Low blaze angle grating for fully dispersive x-ray spectroscopy

We demonstrate fabrication of an ultra-low blaze angle (LBA) grating designed for time-resolved spectroscopy in the x-ray region. A blaze angle of 0.12° was achieved by the groove depth reduction process providing a perfect saw-tooth shape of the grooves. The 200 lines/mm LBA grating exhibited high diffraction efficiency at a photon energy of 8 KeV. Use in a spectrometer would open up dispersive x-ray absorption spectroscopy across a wide energy range including the K edges of 3d transition metals, with much greater efficiency than traditional crystal spectrometers.

Voronov, D. L.↗

Hydrogen Storage Performance of Preferentially Oriented Mg/rGO Hybrids

Chemical interactions on the surface of a functional nanoparticle are closely related to its crystal facets, which can regulate the corresponding energy storage properties like hydrogen absorption. In this study, we reported a one-step growth of magnesium (Mg) particles with both close- and nonclose-packed facets, that is, {0001} and {$2\overline{116}$} planes, on atomically thin reduced graphene oxide (rGO). The detailed microstructures of Mg/rGO hybrids were revealed by X-ray diffraction, selected-area electron diffraction, high-resolution transmission electron microscopy, and fast Fourier transform analysis. Hydrogen storage performance of Mg/rGO hybrids with different orientations varies: Mg with preferential high-index {$2\overline{116}$} crystal surface shows remarkably increased hydrogen absorption up to 6.2 wt % compared with the system exposing no preferentially oriented crystal surfaces showing inferior performance of 5.1 wt % within the first 2 h. First-principles calculations revealed improved hydrogen sorption properties on the {$2\overline{116}$} surface with a lower hydrogen dissociation energy barrier and higher stability of hydrogen atoms than those on the {0001} basal plane, supporting the hydrogen uptake experiment. In addition, the hydrogen penetration energy barrier is found to be much lower than that of {0001} because of low surface atom packing density, which might be the most critical process to the hydrogenation kinetics. Here, the experimental and calculation results present a new handle for regulating the hydrogen storage of metal hydrides by controlled Mg facets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unveiling Charge Transport and Degradation Mechanisms of Aqueous Zn|α-MoO 3 Batteries in Conventional Concentration and Water-in-Salt Electrolytes: A Multi-Modal In Situ and Operando Study

Herein charge storage and transport properties are elucidated and cell degradation mechanisms of rechargeable aqueous Zn|alpha-MoO 3 batteries in three electrolyte systems (3 m ZnSO 4 , 3 m ZnCl 2 , and 30 m ZnCl 2 [12.5 m] water-in-salt (WIS)) are distinguished by a combination of in situ X-ray diffraction (XRD), in situ X-ray absorption spectroscopy (XAS), operando optoelectrochemistry, and operando energy dispersive X-ray diffraction (EDXRD). In conventional concentration 3 m electrolytes, in situ XRD and XAS, as well as ex situ scanning transmission electron microscopy data collectively support Zn 2+ as the primary charge carrier. In addition, these systems are susceptible to cathode dissolution, Zn corrosion coupled with the hydrogen evolution reaction, and the resultant formation of basic zinc salt phases. The multi-modal in situ and operando experimental analyses validate facile H+ intercalation and extraction in concentrated 30 m ZnCl 2 WIS electrolyte. Via operando EDXRD, reaction front and charge transport limitation during discharge and charge in the viscous WIS electrolyte are spatially tracked. Here this work provides new insight into the stability and degradation mechanisms of aqueous zinc batteries during static storage and upon dynamic cycling, and highlights the utility of in situ and operando techniques in understanding the superior stability of WIS electrolytes.

25 ENERGY STORAGE↗

Experiments to Measure the Effect of Tantalum on Critical Systems

Sandia National Laboratories (SNL) and Oak Ridge National Laboratory (ORNL) collaborated to develop a capability to test the epithermal/intermediate cross sections of materials at the SNL critical experiment facility using the Seven Percent Critical Experiment (7uPCX) fuel. As a result, a new set of critical experiments has been designed to target the epithermal cross sections of tantalum (Ta) and is scheduled to be performed at SNL in 2023. These critical experiments will be evaluated for inclusion in the 2024 edition of the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Handbook. The focus of these critical experiments is to measure the effects of Ta on the critical array size. The critical array size will be determined by an approach-to-critical experiment with the number of fuel rods in the array as a free parameter. The core configurations are designed to optimize the reactivity worth of Ta and the overall percentage of Ta absorption rates in the epithermal/intermediate energy range (0.625 eV – 100 keV). The baseline core configuration includes 7uPCX fuel rods set at a triangular pitch of 1.016 cm and a central dry test region that utilizes a cadmium liner for filtering out thermal neutrons. The central test region has locations for 85 Ta rods set at a triangular pitch of 0.813 cm. The Ta reactivity worth for the case with 85 Ta rods is approximately 2.55%, with the percentage of Ta absorption rates within the intermediate energy range at nearly 90%.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Abbreviated Technical Report: Experimentally Interrogating Detonation Chemistry on Sub-Nanosecond to Nanosecond Timescales

Direct experimental measurement of chemical reactions during high explosive detonation remains challenging. Theory and modeling have long preceded experiment in the fundamental physical and chemical kinetic properties of detonation, and experimentation at the relevant timescales are needed to both validate models and provide fundamental understanding of detonation. In this LDRD-ER project, two approaches, x-ray diffraction and core-level x-ray Raman, were developed and used to further experimental capabilities to address this gap. We further developed dynamic x-ray diffraction to directly detect nanodiamond formation during detonation, providing experimental data towards resolving longstanding controversy in the scientific literature, and although the full kinetics have not yet been fully mapped, diamond diffraction appears on the same timescales as detonation soot formation. In the second research thrust, we have developed core-level x-ray Raman for use with high explosives. This technique provides information analogous to x-ray absorption spectroscopy and electron energy loss spectroscopy, but uses inelastic scattering of hard x-rays that can interrogate chemistry around light elements much deeper into the material. The low cross section and requisite high solid angle collection have hindered its use for ultra-fast spectroscopy. We developed and tested a high-q spectrometer which will substantially increase cross section and signal-to-noise, showing this method will also not dramatically alter, compared to x-ray absorption, the most discriminating spectral features of C, N, and O from various high explosives and expected detonation products. We have also used x-ray Raman combined with OCEAN electronic structure calculations to explore dynamic photodegradation mechanisms in PETN and CL-20 explosives. This provides a pathway towards implementing capability to dynamically explore chemistry at an x-ray free electron laser.

36 MATERIALS SCIENCE↗

Mass spectrometry and spectroscopic characterization of a tetrameric photosystem I supercomplex from Leptolyngbya ohadii , a desiccation-tolerant cyanobacterium

Cyanobacteria inhabiting desert biological soil crusts face the harsh conditions of the desert. They evolved a suite of strategies toward desiccation-hydration cycles mixed with high light irradiations, etc. In this study we purified and characterized the structure and function of Photosystem I (PSI) from Leptolyngbya ohadii, a desiccation-tolerant desert cyanobacterium. We discovered that PSI forms tetrameric (PSI-Tet) aggregate. We investigated it by using sucrose density gradient centrifugation, clear native PAGE, high performance liquid chromatography, mass spectrometry (MS), time-resolved fluorescence (TRF) and time-resolved transient absorption (TA) spectroscopy. MS analysis identified the presence of two PsaB and two PsaL proteins in PSI-Tet and uniquely revealed that PsaLs are N-terminally acetylated in contrast to non-modified PsaL in the trimeric PSI from Synechocystis sp. PCC 6803. Chlorophyll (Chl) a fluorescence decay profiles of the PSI-Tet performed at 77 K revealed two emission bands at ∼690 nm and 725 nm with the former appearing only at early delay time. The main fluorescence emission peak, associated with emission from the low energy Chls a, decays within a few nanoseconds. TA studies demonstrated that the 725 nm emission band is associated with low energy Chls a with absorption band clearly resolved at ∼710 nm at 77 K. As a result, our work suggests that the heterogenous composition of PsaBs and PsaL in PSI-Tet is related with the adaptation mechanisms needed to cope with stressful conditions under which this bacterium naturally grows.

59 BASIC BIOLOGICAL SCIENCES↗

Core-excited states of SF 6 probed with soft-x-ray femtosecond transient absorption of vibrational wave packets

A vibrational wavepacket in SF 6 is created by impulsive stimulated Raman scattering with a few-cycle infrared pulse and mapped simultaneously onto five sulfur core-excited states using table-top soft x-ray transient absorption spectroscopy between 170 to 200 eV. The femtosecond vibrations induce real-time energy shifts of the x-ray absorption, whose amplitude depend strongly on the nature of the core-excited state. The pump laser intensity is used to control the number of vibrational states in the superposition, thereby accessing core-excited levels for various extensions of the S-F stretching motion. This enables the determination of the relative core-level potential energy gradients for the symmetric stretching mode, in good agreement with TDDFT calculations. This experiment demonstrates a new means of characterizing core-excited potential energy curves.

74 ATOMIC AND MOLECULAR PHYSICS↗