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At least 361 records · Page 20

Modulating the Mixing Gibbs Free Energy to Enhance Solid–Liquid Phase Separation for High–Performance Organic Solar Cells

Organic solar cells (OSC) feature a hierarchical structure with the electron donor/acceptor layer sandwiched by anode and cathode, which raises the importance of controlling the molecular crystal orientation, domain size, and vertical distribution to facilitate the charge collection at electrodes. However, the similar conjugated backbone of donor/acceptor material and fast film–formation kinetics have led to spinodal–decomposition–orientated phase separation that result in the film presenting an intimately mixed morphology and random molecular orientation. To solve the issue, the mixing Gibbs free energy–triggered solid–liquid phase separation during the film formation process is enhanced by solidifying one component and solvating the other based on a liquid additive. Following the liquid evaporation process, a favorable vertical distribution is obtained. Meanwhile, the prolonged solvation process enlarges the domain size and assists the molecules to diffuse and orient properly, enabling better exciton/charge dynamics during the power conversion processes. As a result, the fabricated devices exhibit a fill factor over 80% and an efficiency of 18.72%, which is one of the top efficiencies for binary OSCs. In conclusion, insights and a methodology is provided here to manipulate the organic donor/acceptor phase separation in terms of mixing Gibbs free energy.

14 SOLAR ENERGY↗

Signal Origin of Electrochemical Strain Microscopy and Link to Local Chemical Distribution in Solid State Electrolytes

Electrochemical strain microscopy (ESM) is a distinguished method to characterize Li-ion mobility in energy materials with extremely high spatial resolution. The exact origin of the cantilever deflection when the technique is applied on solid state electrolytes (SSEs) is currently discussed in the literature. Under-standing local properties and influences on ion mobility in SSEs is of utmost importance to improve such materials for next generation batteries. Here, the exact signal formation process of ESM when applied on sodium super ionic conductor (NASICON)-type SSE containing Na- and Li-ions is investigated. Changes in the dielectric properties, which are linked to the local chemical composition, are found to be responsible for the observed contrast in the deflection of the cantilever instead of a physical volume change as a result of Vegard´s Law. The cantilever response is strongly reduced in areas of high sodium content which is attributed to a reduction of the tip-sample capacitance in comparison to areas with high lithium content. This is the first time a direct link between electrostatic forces in contact mode and local chemical information is demonstrated on SSEs. Furthermore, the results open up new possibilities in information gain since dielectric proper-ties are sensitive to subtle changes in local chemical composition.

36 MATERIALS SCIENCE↗

Polymer coatings on zirconia microspheres via rotating flow fluid dynamics

Conventional tristructural isotropic (TRISO) coatings for nuclear fuels require multi-step and expensive formation processes; any breakage of the coatings may lead to fission species release. Polymer derived ceramic (PDC) coatings can be a suitable alternative to address these issues. In this study, allylhydridopolycarbosilane (SMP-10) coatings were created on yttria stabilized zirconia (YSZ) microspheres using a Rotating Flow Fluid Dynamics (RFFD) coating method. The effects of curing temperature, rotation speed, and coating cycle/time on the coating were analyzed. Surface functionalization of YSZ microspheres with NaOH resulted in good adhesion between the polymer precursor and the YSZ kernel particles. Spectroscopy analysis revealed complete curing of SMP-10 coated YSZ at 160 °C. Rotation speed and coating time significantly affect the coating characteristics. After 3 cycles at lower rotation speed (50 rpm) for 10 min each, the coating obtained was uniform and homogeneous. In comparison, the coating showed almost 10 times less eccentricity at a high rotation speed of 300 rpm. Compared with the coatings prepared at 300 rpm condition, the coatings have higher sphericity and lower eccentricity at 50 rpm. Overall, this study provides a novel and effective route for fabricating and curing SMP-10 precursor coatings on YSZ microspheres.

Ravi, Nivetha [University of Alabama, Birmingham]↗

Atmospheric ice nuclei concentration measurements over a high altitude-station in the Western Ghats, India

Mixed-phase and ice clouds play a significant role in modulating the Indian summer monsoon rainfall, and modeling studies suggest that inaccurate representation of ice nucleating particles (INP) is one of the factors, which have resulted in a deficiency in the prediction of cloud properties and hydrological cycle. We do not understand the ice nucleation mechanisms to represent the ice formation in the model, and therefore more INP measurements at various supercooled temperatures are needed. This study reports for the first time real-time INP concentration at a high altitude station in the Western Ghats region of India, and these results will be used to constrain the ice nucleation parameterizations in the model. The variation of INP for any particular cloud condition can have strong microphysical responses of mixed-phase precipitation formation processes. Also, to improve the representation of heterogeneous ice nucleation, INP measurements of various types of aerosols commonly observed over the Indian region are needed. This study presents, the INP concentrations and daily concentration of non-refractory chemical composition (organics, sulfate, nitrate, ammonium, and chloride), cloud condensation nuclei (CCN), and aerosol size distribution. Spectrometer for Ice Nuclei (SPIN) was operated to measure INP concentration at the mountain site from August to December 2018. INP measurements were performed at three different temperatures (-25, -30, and - 34 °C) in the immersion freezing mode relevant for mixed-phase cloud conditions. The average INP concentrations approximately varied from 0.18 to 12.4 L-1, 0.39 to 24 L-1, 1.1 to 40.2 L-1 at -25, -30, and - 34 °C, respectively. These concentrations are within the concentrations reported in the literature from different regions across the globe. The air mass back trajectory analysis showed that continental air mass contains more INP compared to maritime air mass. The information on INP concentration and chemical characteristics of aerosol will help to improve heterogeneous ice nucleation parameterization in numerical models.

Kumar, Anil V.↗

Discovery of single-atom alloy catalysts for CO 2 -to-methanol reaction by density functional theory calculations

The transformations of CO 2 molecules into valuable products are of increasing interest due to the negative impact of anthropogenic CO 2 emissions on global warming. The CO 2 -to-methanol hydrogenation is an economically profitable reaction of carbon fixation, but it still steps away from widespread industrialization because of the lack of efficient and selective catalysts. Recently, single-atom alloy (SAA) catalysts have been developed to work remarkably in CO 2 hydrogenation reactions. Doping isolated single atoms into metallic catalyst can dramatically alter the catalytic performance of the host. Here, we have performed a screening discovery on Ru and 6 RuX (X = Fe, Co, Ni, Cu, Ir and Pt) SAAs using density functional theory (DFT) computations. We considered 13 possible elementary reactions in 4 possible reaction pathways on Ru and all RuX surfaces. In the computed mechanisms, we found that the formation of *H 2 COOH and *HCOO intermediates plays a critical role in determining catalysts’ activities. Doping Co and Pt isolated single atoms into Ru surface can thermodynamically and kinetically facilitate these intermediates formation processes, eventually promoting the production of methanol. The combination of weak binding and enhanced charge redistribution on RuCo and RuPt surfaces give them improved catalytic activities over pure Ru. This work will ultimately facilitate the discovery and development of SAAs for CO 2 to methanol, serving as guidance to experiments and theoreticians alike.

25 ENERGY STORAGE↗

Molecular insights into Yb(III) speciation in sulfate-bearing hydrothermal fluids from X-ray absorption spectra informed by ab initio molecular dynamics

Rare earth elements (REEs) are critical for advanced technologies, yet in hydrothermal aqueous solutions the molecular level details of their interaction with ligands that control their geochemical transport and deposition remain poorly understood. Here, this study elucidates the coordination behavior of Yb 3+ in sulfate-rich hydrothermal fluids using in situ extended X-ray absorption fine structure (EXAFS) spectroscopy and ab initio molecular dynamics (AIMD) simulations. By integrating multi-angle EXAFS with AIMD-derived constraints, we precisely resolve Yb 3+ coordination structures and ligand interactions under hydrothermal conditions. At room temperature, Yb 3+ is coordinated by five water molecules and two sulfate ligands (coordination number, CN = 8), forming a distorted square antiprism geometry. Increasing temperature induces progressive dehydration, reducing the hydration shell and favoring stronger sulfate complexation. At 200°C, sulfate ligands reorganize around Yb 3+ , shifting its geometry to a capped octahedron (CN = 7). At 300 °C, sulfate binding dominates, leading to structural reorganization that parallels the onset of sulfate mineral precipitation, consistent with the retrograde solubility of REE sulfates. These findings provide direct molecular-scale evidence that sulfate acts as both a transport and deposition ligand, critically influencing REE mobility in geochemical environments. Our results can also help to refine thermodynamic models of REE speciation in high-temperature hydrothermal fluids and improve our understanding of REE ore formation processes in nature.

AIMD↗

Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals

Amorphous inorganic solids are traditionally isotropic, thus, it is believed that they only grow in a non-preferential way without the assistance of regulators, leading to the morphologies of nanospheres or irregular aggregates of nanoparticles. However, in the presence of (ortho)phosphate (Pi) and pyrophosphate ions (PPi) which have synergistic roles in biomineralization, the highly elongated amorphous nanowires (denoted ACPPNs) form in a regulator-free aqueous solution (without templates, additives, organics, etc). Based on thorough characterization and tracking of the formation process (e.g., Cryo-TEM, spherical aberration correction high resolution TEM, solid state NMR, high energy resolution monochromated STEM-EELS), the microstructure and its preferential growth behavior are elucidated. In ACPPNs, amorphous calcium orthophosphate and amorphous calcium pyrophosphate are distributed at separated but close sites. The ACPPNs grow via either the preferential attachment of ~2 nm nanoclusters in a 1-dimension way, or the transformation of bigger nanoparticles, indicating an inherent driving force-governed process. Here, we propose that the anisotropy of ACPPNs microstructure, which is corroborated experimentally, causes their oriented growth. This study proves that, unlike the conventional view, amorphous minerals can form via oriented growth without external regulation, demonstrating a novel insight into the structures and growth behaviors of amorphous minerals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stability-based optimization of ACRT for the growth of CZT by the traveling heater method

Numerical modeling is employed to study the effects of several accelerated crucible rotation technique (ACRT) rotation schedules on the growth of cadmium zinc telluride (CZT) by the traveling heater method (THM). In conjunction with these analyses, a measure is developed to estimate the amplitude of disturbances associated with cellular interface growth morphologies that develop over time and across the melt-solid interface. Furthermore, this disturbance amplitude measure is used to assess the ability of ACRT to stabilize the growth interface and thereby minimize inclusion formation processes. Notably, our analyses reveal that interfacial instability is not well correlated with melt undercooling, explaining why classical ACRT approaches to reduce undercooling by mixing may not stabilize growth. Computations show that interface stability is best achieved via rotation schedules that accentuate outward Ekman flows during spin-up and, during spin-down, eliminate Taylor-Görtler flows and minimize inward Ekman flows.

36 MATERIALS SCIENCE↗

Examining phase separation and crystallization in glasses with X-ray nano-computed tomography

X-ray nano-computed tomography (nano-CT) is a powerful technique to characterize and visualize 3 dimensional (3D) phenomena in complex glasses at the nanoscale. This technique can offer a unique opportunity to explore the intricate morphology of multicomponent glass and glass-ceramic samples, due to its low X-ray energy and high spatial resolution (down to 50 nm). In the current demonstration paper, nano-CT provided insight into crystallization and phase separation, as well as a variety of other phenomena, including corrosion, fracture, and porosity. At scales ranging from 100 to 20 μm, the microstructures of phase separation in borosilicate, complex silicate, and chalcogenide glass compositions were examined. In addition, crystallites present in simulant nuclear waste glasses, volcanic glasses, and other related samples were explored. Nano-CT analysis can add to the understanding of (1) the formation processes, (2) distributions, interactions, and compositions of phases, and (3) the mechanisms, structures, and growth of crystallization and phase separation. Nano-CT offers wide potential in the field of glass science, especially when (1) common characterization methods are insufficient, (2) simple sample preparation is required, (3) 3D rendering is needed, or (4) compelling images of small, complex features are desired.

36 MATERIALS SCIENCE↗

Analysis of soot formation from aviation fuels in laminar counterflow flames

Combustion emissions from aviation contribute to the formation of condensation trail (contrail) that can lead to the formation of anthropogenic cirrus clouds. Ice particles that form contrails are observed to have a linear correlation with soot particle number density. Synthetic aviation fuels (SAFs) offer a promising route to mitigate the production of soot particles while also increasing energy security. Although studies have focused on combustion and spray behavior, the detailed investigation of soot formation processes for different jet fuels and their impact on models for computational fluid dynamics (CFD) applications is not well understood. Moreover, experimental measurements of soot for canonical flames using Synthetic aviation fuels (SAF) for model validation remain scarce. To address this, we use employed the Lawrence Livermore National Laboratory (LLNL) detailed soot model based on the discrete sectional method. Additionally, we develop two reduced chemical mechanisms for Jet-A and Alcohol-to-Jet (C1) that are suitable for turbulent flame simulations and couple them with the Hybrid Method of Moments (HMOM). The detailed and reduced model frameworks are validated against experimental measurements of soot volume fraction (ƒ ν ) from a counterflow burner experiment previously reported in the literature. Given the good agreement between modeling results and experimental measurements for the (1) spatial distribution of ƒ ν and (2) the non-linear variation of peak ƒ ν with strain rate, we further investigate the modeled sub-processes (nucleation, condensation, surface growth, and oxidation) using the LLNL model to analyze the assumptions in the reduced model framework. Furthermore, the results indicate a significant contribution from resonant radicals to the surface growth of soot particles, which are not accounted for in the current implementation of HMOM and could help reconcile soot predictions by the reduced model with observations.

Counterflow↗

Utilization of the LS-APGD microplasma/orbitrap-FTMS booster system for detection and isotopic analysis of neodymium nanoparticles

Detection and isotopic analysis of particle populations has seen rapid growth across several application areas, including environmental analysis, nuclear forensics, and food safety. The ability to characterize the particles' unique elemental and isotopic fingerprints could provide information related to formation, processing history, and transport. Regarding nuclear forensics, isotopic analysis of particles derived from diverse materials is often used as a tool to trace the origin and processing history. Mass spectrometric-based techniques currently used for particle population analysis often suffer from limited mass resolution, particularly when dealing with real-world samples that are affected by isobaric and polyatomic interferences from the matrix. To address these analytical challenges, we propose a novel method utilizing the liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasma ionization source coupled to an ultrahigh resolution Orbitrap mass spectrometer, further enhanced with the FTMS X2T Booster data acquisition and processing unit. The FTMS Booster enables acquisition of extended transient times of up to 3 s, significantly improving mass resolution, thereby reducing or even eliminating the need for prior separation of isobaric or polyatomic interferences. Additionally, the detection of low-abundance isotopes was improved by increasing the signal-to-noise (S/N) ratio. As proof of concept, this study demonstrates the feasibility of the LS-APGD/Orbitrap-FTMS X2T Booster platform for direct analysis using a suspension of well-characterized ∼120 nm neodymium particles. The quality of the isotope ratios values obtained from a few hundred particles were in good agreement with those obtained from homogeneous ionic solutions. These results highlight the potential of the LS-APGD/Orbitrap platform for rapid, accurate, and interference-resilient isotope ratio analysis of particle populations without the need for dissolution and subsequent chemical separations, offering significant advantages for nuclear forensics, safeguards, and environmental applications. The effort here also points to further paths forward, hopefully towards single particle (SP) analysis using microplasma ionization and the ultrahigh resolving power of the Orbitrap mass analyzer.

FTMS X2T booster↗

Laminar and turbulent plasmoid ejection in a laboratory Parker Spiral current sheet

Quasi-periodic plasmoid formation at the tip of magnetic streamer structures is observed to occur in experiments on the Big Red Ball as well as in simulations of these experiments performed with the extended magnetohydrodynamics code, NIMROD. This plasmoid formation is found to occur on a characteristic time scale dependent on pressure gradients and magnetic curvature in both experiment and simulation. Single mode, or laminar, plasmoids exist when the pressure gradient is modest, but give way to turbulent plasmoid ejection when the system drive is higher, which produces plasmoids of many sizes. However, a critical pressure gradient is also observed, below which plasmoids are never formed. A simple heuristic model of this plasmoid formation process is presented and suggested to be a consequence of a dynamic loss of equilibrium in the high- $\beta$ region of the helmet streamer. This model is capable of explaining the periodicity of plasmoids observed in the experiment and simulations, and produces plasmoid periods of 90 minutes when applied to two-dimensional models of solar streamers with a height of $3R_\odot$ . This is consistent with the location and frequency at which periodic plasma blobs have been observed to form by Large Angle and Spectrometric Coronograph and Sun Earth Connection Coronal and Heliospheric Investigation instruments.

Physics↗

Expanding the Design Space of Polymer–Metal Organic Framework (MOF) Gels by Understanding Polymer–MOF Interactions

The fabrication of polymer-MOF composite gels holds great potential to provide emergent properties for drug delivery, environmental remediation, and catalysis. To leverage the full potential of these composites, we investigated how the presence and chemistry of polymers impact MOF formation within the composites and, in turn, how MOFs impact polymer gelation. We show that polymers with a high density of strongly metal-binding carboxylic acids inhibit MOF formation; however, reducing the density of carboxylic acids or substituting them with weaker metal-binding hydroxyl groups permits both MOF formation and gelation within composites. Preparing composites with poly(ethylene glycol) (PEG), which does not bind MOF zirconium (Zr)-oxo clusters, and observing gelation suggests that MOFs can entrap polymer chains to create cross-links in addition to cross-linking them through polymer-Zr-oxo interactions. Both simulations and experiments show composite hydrogels formed with poly(vinyl alcohol) (PVA) to be more stable than those made with PEG, which can reptate through MOF pores upon heating. We demonstrate the generalizability of this composite formation process across different Zr-based MOFs (UiO-66, NU-901, UiO-67, and MOF-525) and by spin-coating gels into conformable films. PVA-UiO-66 composite hydrogels demonstrated high sorption and sustained release of methylene blue relative to the polymer alone (3× loading, 28× slower release), and PVA-MOF-525 composite hydrogels capably sorb the therapeutic peptide Angiotensin 1–7. By understanding the influence of polymer-MOF interactions on the structure and properties of composite gels, this work informs and expands the design space of this emerging class of materials.

36 MATERIALS SCIENCE↗

Electrochemically-Formed Disordered Rock Salt ω-Li x V 9 Mo 6 O 40 as a Fast-Charging Li-Ion Electrode Material

Electrochemically-formed disordered rock salt compounds are an emerging class of Li-ion electrode materials for fast-charging energy storage. However, the specific factors that govern the formation process and the resulting charge storage performance are not well understood. Here, we characterize the transformation mechanism and charge storage properties of an electrochemically-formed disordered rock salt from V 9 Mo 6 O 40 (VMO). The crystal structure of VMO has similar motifs to that of α-V 2 O 5 , a well-studied analogue, but VMO has less mechanical flexibility due to additional corner-sharing octahedra in its structure. As a result, VMO undergoes a single-step transformation pathway, which we characterize through operando X-ray diffraction, and forms an unusual highly distorted lamellar microstructure, as we show with high-resolution transmission electron microscopy. The resulting Li x VMO material shows fast charging and other electrochemical characteristics and performance typical of many nanomaterials, even though the material is composed of relatively large particles.

25 ENERGY STORAGE↗

Volumetric Shaping of Nanoparticle-DNA Crystals by Light-Induced Milling

DNA-programmable self-assembly enables the formation of nanoparticle crystals with controlled lattice symmetry. While this approach offers the formation of complexly ordered nanostructures for optical, mechanical, and biological applications, a mesoscale control over such nanomaterials is limited. Directing the material formation process through the assembly pathway or external fields allows for modulating crystal morphology, but achieving arbitrary morphology remains challenging. Here, we present a photothermal method for shaping 3D DNA-programmable crystals of gold nanoparticles. Through local heating of nanoparticles due to plasmonic light absorption, we induce targeted volumetric dissolution of specifically defined crystal areas with micron-scale accuracy. This technique effectively prescribes crystal shaping and creates arbitrarily shaped voids within crystals. We further investigate both computationally and experimentally the key factors governing volumetric material subtraction. The developed automated light-milling platform enables the fabrication of nanomaterials exhibiting both DNA-programmable nanoscale order and custom-designed mesoscale architecture.

36 MATERIALS SCIENCE↗

A New Cathode Material for a Li–O 2 Battery Based on Lithium Superoxide

Li–O 2 batteries suffer from large charge overpotentials due to the high charge transfer resistance of Li 2 O 2 discharge products. A potential solution to this problem is the development of LiO 2 -based batteries that possess low charge overpotentials due to the lower charge transfer resistance of LiO 2 . In this report, IrLi nanoparticles were synthesized and implemented for the first time as a LiO 2 battery cathode material. The IrLi nanoparticle synthesis was achieved by a temperature- and time-optimized thermal reaction between a precise ratio of iridium nanoparticles and lithium metal. Li–O 2 batteries employing the IrLi-rGO cathodes were cycled up to 100 cycles at moderate current densities with sustained low cell charge potentials (<3.5 V). Further, various characterization techniques, including SEM, DEMS, TEM, Raman, and titration, were used to demonstrate the LiO 2 discharge product and the absence of Li 2 O 2 . On the basis of first-principles calculations, it was concluded that the formation of crystalline LiO 2 can be stabilized by epitaxial growth on the (111) facets of IrLi nanoparticles present on the cathode surface. These findings demonstrate that, in addition to the previously studied Ir 3 Li intermetallic, the IrLi intermetallic also provides a means by which LiO 2 discharge products can be stabilized and confirms the importance of templating for the formation process.

25 ENERGY STORAGE↗

Mechanistic Insights into the Origins of Selectivity in a Cu-Catalyzed C–H Amidation Reaction

The catalytic transformation of C-H to C-N bonds offers rapid access to fine chemicals and high-performance materials, but achieving high selectivity from undirected aminations of unactivated C(sp 3 )-H bonds remains an outstanding challenge. Here, we report the origins of the reactivity and selectivity of a Cu-catalyzed C-H amidation of simple alkanes. Using a combination of experimental and computational mechanistic studies and energy decomposition techniques, we uncover a switch in mechanism from inner-sphere to outer-sphere coupling between alkyl radicals and the active Cu(II) catalyst with increasing substitution of the alkyl radical. The combination of computational predictions and detailed experimental validation shows that simultaneous minimization of both Cu-C covalency and alkyl radical size increases the rate of reductive elimination and that both strongly electron-donating and electron-withdrawing substituents on the catalyst accelerate the selectivity-determining C-N bond formation process as a result of a change in mechanism. These findings offer design principles for the development of improved catalyst scaffolds for radical C-H functionalization reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multi‐Species Energy‐Banded Ions in the Ionosphere During the 21 January 2005 Magnetic Storm: Low‐Altitude Edge of the Warm Plasma Cloak

During the 21–22 January 2005 magnetic storm, the FAST satellite observed warm (< few keV) ions in discrete energy bands on the dayside at ∼3,000 km altitude for more than 6.5 hr. We suggest that the ionospheric energy-banded ions represent the low-altitude edge of the warm plasma cloak observed simultaneously by magnetospheric satellites. This is a clear example of the multi-species ion energy bands (10 eV to several keV) observed during strong magnetic storms by the FAST satellite, stretching from the diffuse auroral region to the plasmapause with lifetimes up to 12 hr. The close association of these energy-banded ions with magnetic storms, their broad latitudinal extent, and the presence of multiple ion species in the same energy band, rather than at the same velocity, indicate that this is a distinct phenomenon from other types of energy-banded ions. During the 21–22 January 2005 magnetic storm, the dayside ion energy band structures, centered at 10 eV (H + ), 40 eV (H + and He + ), and 160 eV (H + , He + , and O + ), were consistent with a “time-of-flight and velocity filter” formation process acting on a near-cusp, impulsive outflow of a <200 eV multi-species ion-source population, poleward and in the same hemisphere as FAST. Understanding the sources and dynamics of warm energy-banded ions and their linkage to the warm plasma cloak is important because during superstorms these ions are transported to L values as low as L ∼ 1.2 in the dawn sector, significantly altering the energetics of the mid-latitude ionosphere.

58 GEOSCIENCES↗