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At least 721 records · Page 40

Tracking Aerosol Convection Interactions Experiment (TRACER) Field Campaign Report

Convective clouds serve a critical role in the Earth’s energy and water cycles through their transport of heat, moisture, momentum, and chemical species through the troposphere driving the global circulation (e.g., Hartmann et al. 1984, Del Genio et al. 2012, Su et al. 2014). On more local scales, convective clouds impact the atmospheric heating profile through diabatic heating effects, removal of water from the atmospheric column through precipitation, and conditioning of the local environment impacting further development of clouds (e.g., Sullivan and Voigt 2021). These critical roles underscore the importance of realistic representation of convective processes across scales of models from large-eddy simulation (LES), to convection-permitting models (CPM; e.g., Kendon et al. 2020, Marinescu et al. 2021), to numerical weather prediction (NWP) models used for operational weather forecasting, to Earth system models used to predict climate sensitivity (Sanderson et al. 2011, Sherwood et al. 2014, Tomassini et al. 2014, Zhao et al. 2016, Cronin et al. 2017). A key component of improving model representation of convective clouds is better quantification and parameterization of updraft microphysics and dynamics, including their interactions with the surrounding environment and storm organization (Bony et al. 2015, Hagos and Houze 2016, Donner et al. 2016, Morrison et al. 2020). Aerosol is an important environmental factor that could affect convective clouds and precipitation since cloud droplet and ice formation processes are initiated by it. Andrae et al. (2004) hypothesized that aerosols associated with increased biomass burning particles acting as cloud condensation nuclei (CCN) result in smaller and more monodisperse cloud droplets leading to suppression of warm rain formation, ultimately leading to more cloud water being lofted above the freezing level based on observations in the Amazon region. The subsequent increase in latent heat release increases the buoyancy of rising convective parcels invigorating the deep convection. This work was followed by a description of the theoretical basis for this “cold-phase invigoration” by Rosenfeld et al. (2008), who argued that it could have a significant effect for deep convective clouds with warm cloud-bases. Several modeling studies (e.g., Khain et al. 2005, 2009, van den Heever et al. 2006, Fan et al. 2007, 2009, 2012, Lee et al. 2008, Storer et al. 2010, Lebo et al. 2012, Storer and van den Heever 2013, Chen et al. 2020, Dagan et al. 2022) have investigated these aerosol-convection interactions and the environmental factors that influence their relative importance and magnitude. More recently, several studies have indicated that “warm-phase invigoration”, the enhancement of convection through condensational heating, also appears to play a role in enhancing both shallow cumuli (Seiki and Nakajima 2014, Saleeby et al 2015) and deeper tropical convection (Lebo and Seinfeld 2011, Khain et al. 2012, Sheffield et al 2015, Fan et al. 2018, Igel and van den Heever 2021), as well as Houston thunderstorms (Fan et al. 2007, 2020). However, still other studies have provided additional evidence of systematic biases in simulated convective outflow ice size distribution properties, which are consistent with a lack of poorly understood secondary ice production within convective updrafts (e.g., Fridlind et al. 2017). To help address these critical gaps in our understanding of cloud processes, aerosol processes and aerosol-cloud interactions, the Tracking Aerosol Convection Interactions Experiment was designed building upon efforts by the Aerosol, Cloud, Precipitation and Climate (ACPC) Initiative (http://acpcintiative.org/), a joint effort of the International Geosphere-Biosphere Programme (IGBP) and the World Climate Research Program (WCRP) that focused on resolving uncertainties in the interactions between aerosol and clouds towards better understanding the role that these interactions play in the climate system. The TRACER campaign was motivated by recommendations from a number of pilot studies undertaken by ACPC (van den Heever et al. 2017, Fridlind et al. 2019, Hu et al. 2019, Fan et al. 2020, Marinescu et al. 2021, Hernandez-Deckers et al. 2022) that pointed towards the southeastern Texas region as a locale where aerosol-convection interactions could be studied owing to the copious occurrence of isolated convection during the summer months accompanied by diverse and significant sources of aerosols from both anthropogenic and natural sources. The TRACER campaign began on 01 October 2021 and extended through 30 September 2022 with an intensive operational period (IOP) during June-September 2022. Three main sites (Table 1) were managed by the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility.

54 ENVIRONMENTAL SCIENCES↗

Aerosol Hygroscopic Growth, Mixing State, and Cloud Condensation Nuclei Activity during TRACER (Field Campaign Report)

Convective clouds play a critical role in the Earth’s climate system. Recent research has shown that a realistic representation of convective processes is critical to constraining climate sensitivity in global climate models. Theoretical and modeling studies showed that aerosols could have strong dynamic feedback to convection in warm and humid environments through enhancing ice-related processes and condensational growth. A few observation-based studies also suggested the influence of aerosols on convective cloud and precipitation properties. However, robust observational quantification of an aerosol effect on convective clouds isolated from other factors remains elusive. Understanding the impact of aerosol on convective clouds requires knowledge of the cloud condensation nuclei (CCN) spectrum, which represents the number of particles that uptake water and form cloud droplets as a function of supersaturation. The water uptake by aerosol is also of critical importance for the direct interaction of aerosol with radiation (i.e., aerosol direct effect) due to light scattering and absorption by aerosol. While both droplet activation under supersaturated conditions (i.e., relative humidity RH > 100%) and the hygroscopic growth under sub-saturated conditions (i.e., RH < 100%) are strongly influenced by particle hygroscopicity, the thermodynamic regimes and measurement methods are quite different. Aerosol particles, especially organic particles, can exhibit higher hygroscopicity for droplet activation than that for hygroscopic growth. In the subsaturated regime, the hygroscopicity of organic particles can also vary strongly with RH. However, global climate models usually treat organic species in aerosols with a constant hygroscopicity, potentially introducing substantial uncertainties in the quantification of aerosol radiative effects.

54 ENVIRONMENTAL SCIENCES↗

Building Stock Models for Embodied Carbon Emissions—A Review of a Nascent Field

Building stock modeling emerges as a critical tool in the strategic reduction of embodied carbon emissions, which is pivotal in reshaping the evolving construction sector. This review provides an overall view of modern methodologies in building stock modeling, homing in on the nuances of embodied carbon analysis in construction. Examining 23 seminal papers, our study delineates two primary modeling paradigms—top-down and bottom-up—each further compartmentalized into five innovative methods. This study points out the challenges of data scarcity and computational demands, advocating for methodological advancements that promise to refine the precision of building stock models. A groundbreaking trend in recent research is the incorporation of machine learning algorithms, which have demonstrated remarkable capacity, improving stock classification accuracy by 25% and urban material quantification by 40%. Furthermore, the application of remote sensing has revolutionized data acquisition, enhancing data richness by a factor of five. This review offers a critical examination of current practices and charts a course toward an environmentally prudent future. It underscores the transformative impact of building stock modeling in driving ecological stewardship in the construction industry, positioning it as a cornerstone in the quest for sustainability and its significant contribution toward the grand vision of an eco-efficient built environment.

Hu, Ming (ORCID:0000000325831161)↗

COSMO: The COronal Solar Magnetism Observatory

The COronal Solar Magnetism Observatory (COSMO) will make the first synoptic, simultaneous measurements of magnetic and plasma properties of the global solar atmosphere, filling crucial gaps in our understanding of the drivers of solar eruptions and the evolution of the coronal magnetic field on time scales from minutes to decades. - COSMO uniquely addresses critical Heliophysics science. With an unparalleled combination of large field of view and high magnetic sensitivity, the 1.5m COSMO Large Coronagraph (LC) opens a new window on coronal magnetism on global scales. Along with K-Coronagraph (K-Cor) middle-corona observations and the Chromosphere and Prominence Magnetometer (ChroMag) observations of the photosphere and chromosphere, these capabilities enable researchers to finally answer crucial questions about solar eruptions, coronal heating/solar wind acceleration, and the solar dynamo. - COSMO is mature. K-Cor has been operating at the Mauna Loa Solar Observatory (MLSO) since 2013 and ChroMag is soon to be deployed. Also at MLSO, the 20cm Upgraded Coronal Multichannel Polarimeter (UCoMP) is proving the power of global coronal spectropolarimetry and whetting the community’s appetite for the unprecedented sensitivity of the LC. - COSMO is low risk. A recent development: the NSF-funded COSMO Site and Design Advancement (COSADA) is a three-year effort currently underway that reduces risk through site selection and final design of the LC. - COSMO has broad community support. The fact that COSMO fills a critical gap in our observational capabilities was recognized in the last Solar and Space Physics Decadal Survey. COSMO builds on the legacy and thriving user base of the MLSO, which has provided global synoptic solar observations to the community for over sixty years. - COSMO is complementary to other solar telescopes. The breakthrough observations obtained by COSMO will not be provided by any other current or proposed observatory, and will enhance the value of other ground- and space-based Heliophysics assets.

Steven Tomczyk↗

Bifurcation and Hysteresis of the Magnetospheric Structure with a varying Southward IMF: Field Topology and Global Three-dimensional Full Particle Simulations

Using a three-dimensional full electromagnetic particle model (EMPM), we have performed global simulations of the interaction between the solar wind and the terrestrial magnetosphere, and have investigated its asymptotic stability. The distance between the dayside magnetopause subsolar point and the Earth center, R(sub mp) is measured, as the intensity of southward IMF |B(sub z)| is slowly varying. Based on the field topology theory, one analyzes the variation of R(sub mp) as a reference index of the dynamics of this interaction, when IMF |B(sub z)| successively increases and decreases to its original value. Two striking results are observed. First, as the IMF |B(sub z)| increases above a critical value, the variation of R(sub mp) suddenly changes (so called 'bifurcation' process in field topology). Above this critical value, the overall magnetic field topology changes drastically and is identified as being the signature of magnetic reconnection at the subsolar point on the magnetopause. Second, this subsolar point recovers its original location R(sub mp) by following different paths as the IMF |B(sub z)| value increases (from zero to a maximum fixed value) and decreases (from this maximum to zero) passing through some critical values. These different paths are the signature of 'hysteresis' effect, and are characteristic of the so-called 'subcritical-type' bifurcation. This hysteresis signature indicates that dissipation processes take place via an energy transfer from the solar wind to the magnetosphere by some irreversible way, which leads to a drastic change in the magnetospheric field topology. This hysteresis is interpreted herein as a consequence of the magnetic reconnection taking place at the dayside magnetopause. The field topology reveals to be a very powerful tool to analyze the signatures of three-dimensional magnetic reconnection without the obligation for determining the mechanisms responsible for, and the consequences of the reconnection on the overall magnetospheric dynamics.

Cai, DongSheng↗

An experimental evaluation of head-up display formats

Three types of head-up display format are investigated. Type 1 is an unreferenced (conventional) flight director, type 2 is a ground referenced flight path display, and type 3 is a ground referenced director. Formats are generated by computer and presented by reflecting collimation against a simulated forward view in flight. Pilots, holding commercial licenses, fly approaches in the instrument flight mode and in a combined instrument and visual flight mode. The approaches are in wind shear with varied conditions of visibility, offset, and turbulence. The displays are equivalent in pure tracking but there is a slight advantage for the unreferenced director in poor conditions. Flight path displays are better for tracking in the combined flight mode, possibly because of poor director control laws and the division of attention between superimposed fields. Workloads is better for the type 2 displays. The flight path and referenced director displays are criticized for effects of symbol motion and field limiting. In the subjective judgment of pilots familiar with the director displays, they are rated clearly better than path displays, with a preference for the unreferenced director. There is a fair division of attention between superimposed fields.

Naish, J. M.↗

A non-intrusive optical (NIO) approach to characterize heliostats in utility-scale power tower plants: Methodology and in-situ validation

No reliable in-situ optical characterization tool is available that can efficiently and accurately measure various optical errors of individual heliostats in a utility-scale power-tower plant. Here, an innovative non-intrusive optical (NIO) approach is proposed to measure mirror surface slope error, mirror facet canting error, and heliostat tracking error based on reflection images using the natural target—the tower—in a heliostat field. The NIO approach adopts various techniques in photogrammetry, reflectometry, and geometrical optics to first determine the camera position and the actual tower position with respect to the heliostat. Then, Snell’s law is applied to find the surface normal at the reflection point or line of a reflection image and derive the surface slope error, mirror facet canting error, and heliostat tracking error accordingly. In addition, an in-situ validation is performed to demonstrate the feasibility of the NIO approach. Analysis with multiple sets of reflection images on one single heliostat of interest demonstrates that the NIO method can achieve a measurement uncertainty of 0.22 mrad for mirror facet slope error (root-mean-square) at the given test conditions. The sensitivity of measurement uncertainty to various parameters will be presented in a separate work. In the future, state-of-the-art unmanned aerial systems (UAS) are planned to perform the efficient image collection with a goal to complete the survey across a utility-scale field of over 10,000 heliostats within one or a few days depending on the number of UASs. The development of the NIO approach is expected to fill the critical gap for successful solar-field operation and maintenance, which is necessary for the global growth of the solar power-tower technology. The NIO approach can also be applied to any relevant industry requiring high-precision mirror surface shape characterization.

14 SOLAR ENERGY↗

Co-sputter deposition of Nb₃Sn layer into SRF cavity using Nb-Sn composite target

Nb₃Sn, with its superior superconducting critical temperature (Tc ~18.3 K) and superheating field (Hsh ~400 mT), is considered a promising material for superconducting radiofrequency (SRF) cavities, offering enhanced cryogenic performance compared to bulk niobium cavities. A Nb₃Sn coating technique has been developed for Nb SRF cavities using co-sputtering of Nb-Sn composite target in a DC cylindrical magnetron sputtering system. The composite target configuration and discharge conditions for co-sputtering were optimized to deposit Nb-Sn films on flat Nb substrates, followed by annealing to form Nb₃Sn. Multiple strategies have been explored to improve the surface homogeneity of the Nb₃Sn coating, including optimizing a two-step annealing process, annealing in Sn vapor, and a light Sn recoating process. A 1.5 µm Nb-Sn co-sputtered film was deposited on the interior of a 2.6 GHz Nb SRF cavity and annealed at 600 °C for 6 h, followed by 950 °C for 1 h. Cryogenic RF testing of the annealed cavity demonstrated a Tc of 17.8 K, confirming the formation of Nb₃Sn. Then, the annealed cavity underwent a light recoating treatment and attained a quality factor (Q0) of 8.5E+08 at 2.0 K.

Accelerator Physics↗

An algorithm for physics informed scan path optimization in additive manufacturing

Site specific microstructure control is a critical research area within the field of additive manufacturing due to its potential to revolutionize part performance. One way to achieve site specific microstructure control is through control of the solidification conditions via the construction of intricate scan paths; however, the search space for such a problem is large. Previous attempts only considered the solidification conditions at the top surface while also requiring either lots of manual-fine tuning or large amounts of computational resources. This paper introduces a general method for scan path optimization which considers the solidification conditions in the bulk of the material without an increase in computational expense. This method consists of three core components:1. A heat transfer model for simulating the temperature field at a given time.2. A surrogate model which takes scan pattern information and temperature data and predicts the solidification conditions of the bulk as well as the meltpool depths for a spot melt.3. A decision algorithm to decide which spot melt should be printed next based on the outputs of the surrogate model.Each of these components can be changed without changing the overall method. Within this work, this method is applied in the creation of an algorithm containing a semi-analytic heat transfer model to simulate the temperature field, a fully convolutional neural network (FCNN) as the surrogate model, and a greedy decision algorithm. The resulting algorithm produced complex scan patterns which gave strong results for simulated microstructure control.

36 MATERIALS SCIENCE↗

Field-scale estimation of soil properties from spectral induced polarization tomography

Estimates of soil properties such as Cation Exchange Capacity (CEC), water content, grain size characteristics, and permeability are important in geotechnical engineering, water resources, and agriculture. We develop a non-intrusive approach to estimate these properties in the field using spectral induced polarization (SIP) tomography. This geophysical method provides information about the frequency dependence of the complex electrical conductivity of porous media. Using 18 soil samples collected from a Bordeaux vineyard, we first conducted a laboratory study using SIP over the frequency range 10 mHz-45 kHz. The laboratory data were used to confirm the accuracy of a recently developed dynamic Stern layer petrophysical model. The results are consistent with published values from previous works using soils. A comparison was made by comparing the field complex conductivity spectra and the experimental data at two locations where core samples were obtained. The model was then used in concert with field data to image the spatial distribution of CEC, water content, permeability, and mean grain size along a vineyard transect. For clay and sandy textures found in the field, measured and estimated CEC agree rather well (from 6 to 40% discrepancy). Furthermore, our approach provides an efficient way to estimate important soil properties in a non-invasive manner, in high resolution, and over field-relevant scales of the critical zone of the Earth.

54 ENVIRONMENTAL SCIENCES↗

Performance degradation due to anodic failure mechanisms in lithium-ion batteries

Here, we report a mechano-chemical model for anodic degradation during fast-charging of nickel-manganese-cobalt (NMC)/graphite (C) cell due to SEI growth, lithium plating/stripping, dead lithium storage, and film fracture of composite SEI and plated lithium film. Degradation of the battery is analyzed for a range of charging rates from 1 to 6 C-rates, and the influence of plating mechanisms – lithium plating and dead lithium deposition and recovery during stripping – on the film resistance of the anode are accounted for in the model. Dynamic evolution of the interfacial properties is modeled using rule-of-mixture approach. Model predictions of plating associated stress fields are used to compute critical energy release rate for film cracking. The results indicate an increased tendency of fracture for thinner SEI film with lithium plating at higher charging rates. The process of reforming the cracked film absorbs a significant portion of the electrode current thereby reducing the cell capacity and plating efficiency. The mechano-chemical model provides an extensive analytical framework for understanding the synergistic coupling of anodic degradation mechanisms, prognosticating conditions of SEI failure, and evaluating the capacity fade and efficiency of lithium-ion battery.

25 ENERGY STORAGE↗

Hot QCD phase diagram from holographic Einstein–Maxwell–Dilaton models

In this review, we provide an up-to-date account of quantitative holographic descriptions of the strongly coupled quark-gluon plasma (QGP) produced in heavy-ion collisions, based on the class of gauge-gravity Einstein-Maxwell-Dilaton (EMD) models. Holography is employed to tentatively map the QCD phase diagram at finite temperature onto a dual theory of charged, asymptotically AdS black holes in 5D. With a quantitative focus on the hot QCD phase diagram, the EMD models reviewed are adjusted to describe lattice results for the finite-temperature QCD equation of state, with 2+1 flavors and physical quark masses, at zero chemical potential and vanishing electromagnetic fields. The predictive power of EMD models is tested by quantitatively comparing their predictions for the hot QCD equation of state at nonzero baryon density and the corresponding state-of-the-art lattice QCD results. The shear and bulk viscosities predicted by these EMD models are also compared to the corresponding profiles favored by the latest phenomenological multistage models describing different heavy-ion data. We report preliminary results from a Bayesian analysis which provide systematic evidence that lattice results at finite temperature and zero baryon density strongly constrains the free parameters of EMD models. Remarkably, the set of parameters constrained by lattice results at zero chemical potential produces EMD models in quantitative agreement with lattice QCD results also at finite baryon density. We also review results for equilibrium and transport properties from magnetic EMD models, describing the QGP at finite temperatures and magnetic fields. Lastly, we provide a critical assessment of the main limitations and drawbacks of the holographic models reviewed in the present work, and point out some perspectives we believe are of fundamental importance for future developments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

High-resolution 3D strain and orientation mapping within a grain of a directed energy deposition laser additively manufactured superalloy

The industrialization of Laser Additive Manufacturing (LAM) is challenged by the undesirable microstructures and high residual stresses originating from the fast and complex solidification process. Non-destructive assessment of the mechanical performance controlling deformation patterning is therefore critical. Here, we use Dark Field X-ray Microscopy (DFXM) to map the 3D subsurface intragranular orientation and strain variations throughout a surface-breaking grain within a directed energy deposition nickel superalloy. DFXM results reveal a highly heterogenous 3D microstructure in terms of the local orientation and lattice strain. The grain comprises ≈ 5 μm-sized cells with alternating strain states, as high as 5 x10 -3 , and orientation differences <0.5°. The DFXM results are compared to Electron Backscatter Diffraction measurements of the same grain from its cut-off surface. Here, we discuss the microstructure developments during LAM, rationalising the development of the deformation patterning from the extreme thermal gradients during processing and the susceptibility for solute segregation.

36 MATERIALS SCIENCE↗

Size- and Phase-Controlled Nanometer-Thick ß-Ga2O3 Films with Green Photoluminescence for Optoelectronic Applications

Realization and optimization of the tunable/enhanced optical properties is critical to further advance the field of optoelectronics, photonics, and nano-electronics. In this context, here, we demonstrate green-emission characteristics with a ~30 fold enhancement in selectively engineered nanocrystalline Ga2O3 with a control over size, phase and interface nanostructure. Pulsed-laser-deposited ß-phase Ga2O3 films with an average crystallite size of ~9 nm along with a highly dense, close-compact nano-columnar structure with lowest possible defect density facilitates the thirty-fold enhancement in the photoluminescence (PL) intensity in green-region. Enhanced PL-emission in the optimized, engineered nano-architecture sheds light in designing Ga2O3-materials for promising future optoelectronic/photocatalytic applications.

Ga2O3, Nanocrystalline Films, Pulsed-Laser Deposit↗

Josephson detection of time-reversal symmetry broken superconductivity in SnTe nanowires

A Josephson junction (JJ) couples the supercurrent flowing between two weakly linked superconductors to the phase difference between them via a current-phase relation (CPR). While a sinusoidal CPR is expected for conventional junctions with insulating weak links, devices made from some exotic materials may give rise to unconventional CPRs and unusual Josephson effects. In this work, we present such a case: we investigate the proximity-induced superconductivity in SnTe nanowires by incorporating them as weak links in JJs and observe a deviation from the standard CPR. We report on indications of an unexpected breaking of time-reversal symmetry in these devices, detailing the unconventional characteristics that reveal this behavior. These include an asymmetric critical current in the DC Josephson effect, a prominent second harmonic in the AC Josephson effect, and a magnetic diffraction pattern with a minimum in critical current at zero magnetic field. The analysis examines how multiband effects and the experimentally visualized ferroelectric domain walls give rise to this behavior, giving insight into the Josephson effect in materials that possess ferroelectricity and/or multiband superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Machine learning-accelerated discovery of heat-resistant polysulfates for electrostatic energy storage

The development of heat-resistant dielectric polymers that withstand intense electric fields at high temperatures is critical for electrification. Balancing thermal stability and electrical insulation, however, is exceptionally challenging as these properties are often inversely correlated. A traditional intuition-driven polymer design approach results in a slow discovery loop that limits breakthroughs. Here we present a machine learning-driven strategy to rapidly identify high-performance, heat-resistant polymers. A trustworthy feed-forward neural network is trained to predict key proxy parameters and down select polymer candidates from a library of nearly 50,000 polysulfates. The highly efficient and modular sulfur fluoride exchange click chemistry enables successful synthesis and validation of selected candidates. A polysulfate featuring a 9,9-di(naphthalene)-fluorene repeat unit exhibits excellent thermal resilience and achieves ultrahigh discharged energy density with over 90% efficiency at 200 °C. Its exceptional cycling stability underscores its promise for applications in demanding electrified environments.

Li, He↗

Pt-Ligand single-atom catalysts: tuning activity by oxide support defect density

The support–metal interaction is an important element of heterogeneous catalyst design and is particularly critical for the rapidly growing field of single-atom catalysts (SACs). In this work, we investigate the impact of varying the defect density of the titania support on metal–organic Pt SACs for hydrosilylation reactions. Pt SACs are decorated on the powder titania support, employing a metal–ligand interaction with a dipyridyl-tetrazine ligand (DPTZ). The single-atom nature of Pt is verified by X-ray absorption spectroscopy (XAS) on both pristine and defective titania surfaces. These Pt species have a +2 oxidation state and are stabilized by bonding with DPTZ, surface oxygen, and residual chloride from the metal precursor. The catalytic activity is evaluated for the alkene hydrosilylation reaction and it is discovered that the activity of Pt-ligand is positively correlated with the defect density of the titania support. The turn-over number (TON) is calculated to be 12 530 for Pt SACs on a defective surface, which is significantly higher than Pt SACs on a pristine titania surface (830) for the same reaction period (10 min) under the same conditions (70 °C). We ascribe the high activity of Pt SACs on defective titania surfaces to two aspects: the coordination of Pt with more chloride than on pristine titania surfaces, which shortens the induction period of the reaction, and the preferential dispersion of Pt–DPTZ units on defective regions of titania surfaces, allowing facile contact between Pt sites and reactants. The supported Pt–DPTZ SACs show high stability through multiple cycles of batch reactions. This work demonstrates an efficient approach to improve the activity and stability of SACs by optimizing the metal–support interaction, which can also be applied to other oxide surfaces to further develop next-generation heterogeneous single-atom catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of uranyl complexation on the reaction kinetics of the dodecane radical cation with used nuclear fuel extraction ligands (TBP, DEHBA, and DEHiBA)

Specialized extractant ligands – such as tri-butyl phosphate (TBP), N,N-di-(2-ethylhexyl)butyramide (DEHBA), and N,N-di-2-ethylhexylisobutryamide (DEHiBA) – have been developed for the recovery of uranium from used nuclear fuel by reprocessing solvent extraction technologies. These ligands must function in the presence of an intense multi-component radiation field, and thus it is critical that their radiolytic behaviour be thoroughly evaluated. This is especially true for their metal complexes, where there is negligible information on the influence of complexation on radiolytic reactivity, despite the prevalence of metal complexes in used nuclear fuel reprocessing solvent systems. Here we present a kinetic investigation into the effect of uranyl (UO 2 2+ ) complexation on the reaction kinetics of the dodecane radical cation (RH˙ + ) with TBP, DEHBA, and DEHiBA. Complexation had negligible effect on the reaction of RH˙ + with TBP, for which a second-order rate coefficient (k) of (1.3 ± 0.1) × 10 10 M -1 s -1 was measured. For DEHBA and DEHiBA, UO 2 2+ complexation afforded an increase in their respective rate coefficients: k(RH˙ + + [UO 2 (NO 3 ) 2 (DEHBA) 2 ]) = (2.5 ± 0.1) × 10 10 M -1 s -1 and k(RH˙ + + [UO 2 (NO 3 ) 2 (DEHiBA) 2 ]) = (1.6 ± 0.1) × 10 10 M -1 s -1 . This enhancement with complexation is indicative of an alternative RH˙ + reaction pathway, which is more readily accessible for [UO 2 (NO 3 ) 2 (DEHBA) 2 ] as it exhibited a much larger kinetic enhancement than [UO 2 (NO 3 ) 2 (DEHiBA) 2 ], 2.6× vs. 1.4×, respectively. Complementary quantum mechanical calculations suggests that the difference in reaction kinetic enhancement between TBP and DEHBA/DEHiBA is attributed to a combination of reaction pathway (electron/hole transfer vs. proton transfer) energetics and electron density distribution, wherein attendant nitrate counter anions effectively ‘shield’ TBP from RH˙ + electron transfer processes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗