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At least 559 records · Page 31

Adsorptive behavior of poly (vinylidene fluoride) membranes for the recovery of lignin-derived hydrophobic deep eutectic solvents

Abstract Recently, membrane technology has gained significant traction as an energy-efficient alternative to traditional thermal processes for solvent recovery. Deep eutectic solvents (DESs) have emerged as sustainable alternatives to conventional organic solvents, yet a systematic methodology for selecting compatible membrane materials for their recovery remains underdeveloped. This study established a predictive framework for membrane material selection in hydrophobic DES applications using Hansen Solubility Parameters (HSP) with inverted criteria targeting materials with relative energy difference (RED) values greater than 1.0. Flat sheet membranes were fabricated via the non-solvent induced phase separation (NIPS) technique. Four NIPS fabricated polymer membranes were evaluated: polysulfone, cellulose acetate, polyvinylidene fluoride (PVDF) fabricated with polyethylene glycol (PEG) as a pore-forming agent, and polybenzimidazole (PBI). The HSP approach successfully predicted membrane-solvent compatibility, with polysulfone (RED = 0.6) and cellulose acetate (RED = 0.9) dissolving completely within 24 h, while PVDF (RED = 1.9) and PBI (RED = 1.1) maintained structural integrity throughout a 7-day exposure period. Furthermore, PVDF demonstrated superior performance with minimal weight gain (3.0%), hydrophobic surface characteristics (122° water contact angle), and enhanced mechanical properties following DES exposure. Comprehensive chemical and morphological characterization confirmed PVDF’s chemical stability and revealed a surface-selective interaction mechanism involving simultaneous PEG (pore-forming agent) extraction and DES component adsorption. Adsorption kinetics followed pseudo-first-order behavior with reversible characteristics, best described by the Temkin isotherm model (R² = 0.9987). PVDF membranes-maintained separation functionality with average lignin rejection (75.2 ± 7.69%) and demonstrated filtration permeability of 2.0 ± 0.34 LMH/bar. This methodology provides a rational approach for membrane selection in emerging solvent systems, contributing to the advancement of sustainable separation technologies for DES-based biomass processing applications.

Science & Technology - Other Topics↗

Azobenzene-based sinusoidal surface topography drives focal adhesion confinement and guides collective migration of epithelial cells

Surface topography is a key parameter in regulating the morphology and behavior of single cells. At multicellular level, coordinated cell displacements drive many biological events such as embryonic morphogenesis. However, the effect of surface topography on collective migration of epithelium has not been studied in detail. Mastering the connection between surface features and collective cellular behaviour is highly important for novel approaches in tissue engineering and repair. Herein, we used photopatterned microtopographies on azobenzene-containing materials and showed that smooth topographical cues with proper period and orientation can efficiently orchestrate cell alignment in growing epithelium. Furthermore, the experimental system allowed us to investigate how the orientation of the topographical features can alter the speed of wound closure in vitro. Our findings indicate that the extracellular microenvironment topography coordinates their focal adhesion distribution and alignment. These topographic cues are able to guide the collective migration of multicellular systems, even when cell–cell junctions are disrupted.

59 BASIC BIOLOGICAL SCIENCES↗

Determining flow directions in river channel networks using planform morphology and topology

Abstract. The abundance of global, remotely sensed surface water observations has accelerated efforts toward characterizing and modeling how water moves across the Earth's surface through complex channel networks. In particular, deltas and braided river channel networks may contain thousands of links that route water, sediment, and nutrients across landscapes. In order to model flows through channel networks and characterize network structure, the direction of flow for each link within the network must be known. In this work, we propose a rapid, automatic, and objective method to identify flow directions for all links of a channel network using only remotely sensed imagery and knowledge of the network's inlet and outlet locations. We designed a suite of direction-predicting algorithms (DPAs), each of which exploits a particular morphologic characteristic of the channel network to provide a prediction of a link's flow direction. DPAs were chained together to create “recipes”, or algorithms that set all the flow directions of a channel network. Separate recipes were built for deltas and braided rivers and applied to seven delta and two braided river channel networks. Across all nine channel networks, the recipe-predicted flow directions agreed with expert judgement for 97 % of all tested links, and most disagreements were attributed to unusual channel network topologies that can easily be accounted for by pre-seeding critical links with known flow directions. Our results highlight the (non)universality of process–form relationships across deltas and braided rivers.

54 ENVIRONMENTAL SCIENCES↗

Dynamic Surface Restructuring in Cu(Au) Alloys Driven by Oxygen-Mediated Au Mobility

Alloying plays a crucial role in tuning the surface properties of metals, but the atomic-level mechanisms by which alloying elements influence surface structure dynamics under reactive conditions remain elusive. Using Cu(Au) in oxidizing environments as a model system, we reveal a dynamic oxygen-induced transformation of the topmost atomic layer into a periodically hill-and-valley morphology with reversible switching between undulated and flattened surface states. These interconversions are driven by the retreat of surface Au to the subsurface during oxygen adsorption and its resegregation to the surface upon oxygen desorption. This cyclical mobility establishes a feedback loop, allowing the surface to dynamically reconfigure in response to changes in the oxygen pressure. The results offer a broadly applicable framework for understanding atomic-scale surface restructuring in alloy systems, where differences in the chemical reactivity of alloying elements drive dynamic redistribution between surface and subsurface regions. As a result, this dynamic coupling has practical implications for designing corrosion-resistant coatings and metastable nanostructures with tunable catalytic properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Nanowire-Based Materials as Coke-Resistant Catalyst Supports for Dry Methane Reforming

In this paper, nanowire-supported catalysts loaded with nickel are shown to be coke resistant compared to nanoparticle-supported catalysts. Specifically, Ni-loaded titania-based nanowire catalysts were tested with the dry methane reforming process in a laboratory-scale continuous packed-bed atmospheric reactor. The CO 2 conversion rate stayed above 90% for over 30 h on stream under coke-promoting conditions, such as high flow rates, low temperatures, and a high ratio of CH 4 to CO 2 . The coke (C x H y , x>>y) on the spent catalyst surface for both nanowire- and nanoparticle-supported catalysts was characterized by TGA, temperature-programmed reduction (TPR), and electron microscopy (SEM/TEM/EDS), and it was revealed that the types of carbon species present and their distribution over the morphology-enhanced materials played a major role in the deactivation. The CO 2 conversion activity of Ni supported on titania nanoparticles was reduced from ~80% to less than 72% in 30 h due to the formation of a graphitic coke formation. On the other hand, Ni particles supported on nanowires exhibited cube-octahedral morphologies, with a high density of non- (111) surface sites responsible for the increased activity and reduced graphitic coke deposition, giving a sustained and stable catalytic activity during a long time-on-stream experiment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Meteorological Factors on the Mesoscale Morphology of Cloud Streets during a Cold-Air Outbreak over the Western North Atlantic

We report postfrontal clouds (PFC) are ubiquitous in the marine boundary layer, and their morphology is essential to estimating the radiation budget in weather and climate models. Here we examine the roles of sea surface temperature (SST) and meteorological factors in controlling the mesoscale morphology and evolution of shallow clouds associated with a cold-air outbreak that occurred on 1 March 2020 during phase I of the Aerosol Cloud Meteorology Interactions over the Western Atlantic Experiment (ACTIVATE). Our results show that the simulated PFC structure and ambient conditions by the Weather Research and Forecasting (WRF) Model are generally consistent with observations from GOES-16 and dropsonde measurements. We also examine the thermodynamical and dynamical influences in the cloud mesoscale morphology using WRF sensitivity experiments driven by two meteorological forcing datasets with different domain-mean SST and spatial gradients, which lead to dissimilar values of hydrometeor water path and cloud core fraction. The SST from ERA5 leads to weaker stability and higher inversion height than the SST from FNL does. In addition, the use of large-scale meteorological forcings from ERA5 yields a distinctive time evolution of wind direction shear in the inner domain, which favors the formation and persistence of longer cloud rolls. Both factors contribute to a change in the time evolution of domain-mean water path and cloud core fraction of cloud streets. Our study takes advantage of the simulation driven by the differences between two large-scale forcing datasets to illustrate the importance of SST and wind direction shear in the cloud street morphology in a realistic scenario.

54 ENVIRONMENTAL SCIENCES↗

"Soiling, Cleaning, and Abrasion: The Results of the Five-Year Photovoltaic Glass Coating Field Study" [Slides]

External contamination ("soiling") of the incident surface is a major limiting factor for solar technologies. A 5-year field glass coupon study was conducted to better understand external contamination and its effects; compare cleaning methods and the use of preventative coatings; and explore the abrasion resulting from cleaning to advise on accelerated abrasion testing. Test sites included the cities of Dubai (UAE), Kuwait City (Kuwait), Mesa (AZ), Mumbai (India), and Sacramento (CA). Through the 5-year cumulative study, dry brush, water spray, and wet sponge and squeegee cleaning methods were compared to no cleaning. Optical microscopy was used to obtain images, including representative color images, grayscale images for object analysis, and oblique images for coating integrity assessment. A thresholding protocol was developed to analyze and distinguish specimens using the ImageJ software. Optical performance was quantified using a spectrophotometer, including comprehensive optical characterization (transmittance, reflectance, and absorptance in addition to forward- and back-scattering). Atomic force microscopy was used to verify the abrasion damage morphology, including the width and depth of surface scratches. Analysis of the results included correlation of optical performance and particle area coverage, rank order (by coating or location), and the acceleration factor for abrasion damage. The efficacy of external cleaning was more readily distinguished from the effectiveness of antisoiling coatings. The acceleration factor for dry brush cleaning of a porous silica coating was found to be on the order of unity.

14 SOLAR ENERGY↗

Supercritical preparation of doped (111) facetted nickel oxide for the oxygen evolution reaction

Green hydrogen is of great interest as a replacement for traditional fossil fuels in a variety of energy applications. However, due to the poor kinetics present in the oxygen evolution reaction (OER) half-reaction, nanostructured catalysts are needed to reduce the reaction overpotential. Nickel oxide has previously been shown to be a promising alternative to expensive Pt-group based catalysts for the OER in alkaline media. Herein, facetted NiO nanosheets have been doped with Fe, Mn, or Co to reduce its catalytic overpotential for the OER. A supercritical synthesis process was used to promote the mass transport of the reactants while preserving catalytic surface area. Microscopy, diffraction, spectroscopy, and adsorption techniques were used to understand the morphological changes resulting from the inclusion of each dopant, as well as characterize the surface chemistry presented by the doped (111) facet. The pH was found to affect the properties of mixing due to difference in hydrolysis rates and catalysis of the hydrolysis/condensation. The dopants exhibited distinct effects on OER activity: Mn increased the overpotential to 742 mV vs. RHE, while Co and Fe reduced it to 502 mV and 457 mV, respectively. In summary, a straightforward and novel synthesis method is presented to prepare doped NiO(111) nanosheets, and their surface characteristics are explored to understand their varied electrochemical performances.

08 HYDROGEN↗

An Overview of Atmospheric Features Over the Western North Atlantic Ocean and North American East Coast—Part 2: Circulation, Boundary Layer, and Clouds

The Western North Atlantic Ocean (WNAO) is a complex land-ocean-atmosphere system that experiences a wide range of atmospheric phenomena, which in turn drive unique aerosol transport pathways, cloud morphologies, and boundary layer variability. This work, Part 2 of a 2-part paper series, provides an overview of the atmospheric circulation, boundary layer variability, three-dimensional cloud structure, and precipitation over the WNAO; the companion paper (Part 1) focused on chemical characterization of aerosol, gas, and wet deposition. Seasonal changes in the circulation and sea surface temperature explain a clear transition in cloud morphologies from small shallow cumulus clouds, convective clouds, and tropical storms in summer, to stratus/stratocumulus and multi-layer cloud systems associated with winter storms. Synoptic variability in cloud fields is estimated using satellite-based weather states, and the role of postfrontal conditions (cold-air outbreaks) in the development of stratiform clouds is further analyzed. Precipitation is persistent over the ocean, with a regional peak over the Gulf Stream path, where offshore sea surface temperature gradients are large and surface fluxes reach a regional peak. Satellite data show a clear annual cycle in cloud droplet number concentration along the coast in winter, and minima in summer, suggesting a marked annual cycle in aerosol-cloud interactions. The performance of four climate models are assessed against satellite cloud retrievals. The models qualitatively reproduce the annual cycle in cloud cover and liquid water path, but with large discrepancies across models, especially in the extra-tropics. The paper concludes with a summary of outstanding issues and recommendations for future work.

54 ENVIRONMENTAL SCIENCES↗

Partitioning behavior and mechanisms of rare earth elements during precipitation in acid mine drainage

Rare earth elements (REEs) are frequently found concentrated in acid mine drainage (AMD). The recovery of REEs from AMD has been successfully achieved using selective chemical precipitation. However, a portion of the REEs is often lost to the precipitates of the dominant metal contaminant ions. To better understand the REE partitioning behavior and mechanisms during the precipitation process, a systematic study was performed on both natural and synthetic AMD solutions. Precipitation test results show that REE removal was noticeably elevated at pH 4.0 after adding H 2 O 2 to convert ferrous to ferric ions, causing nearly complete precipitation of iron. Solution equilibrium calculations suggested that the REE removal increase was realized through adsorption onto the surfaces of the ferric precipitates. The presence of aluminum species in the solutions reduced the adsorption of REEs on the ferric precipitates. Based on electro-kinetic test results, it was concluded that aluminum species neutralize the negative surface charge of the ferric precipitates and compete with REEs for the adsorption active sites. The presence of ferrous ions in the solutions reduced REE adsorption on the aluminum precipitates at lower pH values (e.g., 5.0) due to competitive adsorption. However, at higher pH values (e.g., 6.0), REE removal to the precipitate product increased due to the precipitation of ferrous ions. Additionally, to the electro-kinetic tests and solution equilibrium calculations, mineralogy characterization, specific surface area measurement, particle size analysis, and morphology analysis were also conducted to investigate and identify the partitioning mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlled thermal pre-treatment of ZMG232G10® for corrosion mitigation under simulated SOFC interconnect exposure conditions

The IT-SOFC candidate interconnect material ZMG232G10® was thermally pre-treated in air and in H 2 – 3% H 2 O to mitigate dual atmosphere corrosion. Bare and pre-treated steel samples were exposed to a dual atmosphere exposure condition (dry air/metal/4% H 2 – N 2 (bal.) + 3% H 2 O) for 500h at 600°C. Corrosion products and oxide morphology developed on the air-exposed surfaces were analyzed. Pre-treatments of the metal in oxidizing (air) and reducing (H 2 – 3% H 2 O) gas atmospheres provide improved passivation against dual atmosphere corrosion compared to bare steel. Further, the uniform and iron-free oxide scale developed during the pre-treatment of alloy in the low pO 2 H 2 – 3% H 2 O gas atmosphere provides an effective diffusion barrier against the outward transport of cations and oxidation of iron observed under dual atmosphere conditions.

36 MATERIALS SCIENCE↗

Intense Pulse Light Annealing of Perovskite Photovoltaics Using Gradient Flashes

Perovskite solar cells (PSCs) have been fabricated through high-speed and low-cost depositions but often require long annealing. Intense pulse light (IPL) can anneal thin films in seconds after deposition by inducing very high temperatures lasting for milliseconds, and multiple flashes can be used to tune the temperature profile. In this study, a gradient flash annealing (GFA) approach is introduced and compared to uniform flash annealing (UFA) by investigating the crystallinity, morphology, and phase evolution of the CH 3 NH 3 PbI 3 perovskite films and their impact on PSC performance. Unlike UFA, low-intensity pulsed irradiation during the pre-annealing stage of GFA played a significant role on enhancing the PSC performance by forming pure-phase CH 3 NH 3 PbI 3 perovskite thin films with superior morphology and high crystallinity. To understand the kinetics, a transient thermal simulation using ANSYS was developed and confirmed with an experimental setup. The results combined with microscopy and spectrophotometry were used to visualize how duration, delay time, photon flux, and flash count parameters participated in crystallization, phase, and morphology evolution. The IPL annealing induced rapid surface temperature increase, reaching as high as 800 °C, while produced well-developed and bound perovskite grains without any surface defects in an uncontrolled ambient environment with high humidity (>60%). The study resulted in PSCs with maximum efficiency and fill factor of 9.27 and 69.92% for the UFA and 11.75 and 68% when annealed through the GFA approach, respectively. Lastly, this work utilized IPL as the sole thermal source for post-deposition annealing to rapidly fabricate efficient PSCs in only 10 s, which opens the pathway for high-speed, low-cost, and large-scale automated fabrication of perovskite photovoltaics and semiconductors.

14 SOLAR ENERGY↗

Revisiting the Effects of Seed Liquid Water Content on Isoprene Secondary Organic Aerosol Growth

Aerosol liquid water content (LWC) has been shown to enhance partitioning of water-soluble oxygenated organic vapors into the aerosol particles and facilitate aqueous chemistry, impact SOA formation, composition, and physicochemical properties. Here, this study examines the effect of aerosol liquid water content (LWC) on isoprene SOA formation using effloresced and deliquesced ammonium sulfate ((NH 4 ) 2 SO 4 ) and sodium chloride (NaCl) seed particles in an environmental chamber with photo-oxidation extending over hours under moderate relative humidity (50%-60%). Our findings indicate that isoprene SOA mass yield is not significantly influenced (p value >> 0.05) by the phase state or the chemical identity of the seed particles within a 3–4-hour reaction time scale. Detailed molecular analysis using advanced high resolution mass spectrometry indicates that while both effloresced and deliquesced seed types produced similar molecular formula distributions, deliquesced (NH 4 ) 2 SO 4 slightly favored the production of less volatile compounds. Depth-profiling analysis by single particle mass spectrometry confirmed that isoprene SOA predominantly located on the surfaces of particles with core-shell morphologies, with partial dissolution of the effloresced inorganic salt observed even below the deliquescence relative humidity (DRH) of salt. This finding suggests that assuming dry salt core particles do not interact with SOA coatings, based on salt deliquescence points, may overlook important aqueous chemistry. These results emphasize the critical role of reaction time scale and mixing state on SOA formation and call for further research to understand LWC effects on SOA from different precursors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Adsorbate chemical environment-based machine learning framework for heterogeneous catalysis

Abstract Heterogeneous catalytic reactions are influenced by a subtle interplay of atomic-scale factors, ranging from the catalysts’ local morphology to the presence of high adsorbate coverages. Describing such phenomena via computational models requires generation and analysis of a large space of atomic configurations. To address this challenge, we present Adsorbate Chemical Environment-based Graph Convolution Neural Network (ACE-GCN), a screening workflow that accounts for atomistic configurations comprising diverse adsorbates, binding locations, coordination environments, and substrate morphologies. Using this workflow, we develop catalyst surface models for two illustrative systems: (i) NO adsorbed on a Pt 3 Sn(111) alloy surface, of interest for nitrate electroreduction processes, where high adsorbate coverages combined with low symmetry of the alloy substrate produce a large configurational space, and (ii) OH* adsorbed on a stepped Pt(221) facet, of relevance to the Oxygen Reduction Reaction, where configurational complexity results from the presence of irregular crystal surfaces, high adsorbate coverages, and directionally-dependent adsorbate-adsorbate interactions. In both cases, the ACE-GCN model, trained on a fraction (~10%) of the total DFT-relaxed configurations, successfully describes trends in the relative stabilities of unrelaxed atomic configurations sampled from a large configurational space. This approach is expected to accelerate development of rigorous descriptions of catalyst surfaces under in-situ conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Wox3 -patterning module organizes planar growth in grass leaves and ligules

Grass leaves develop from a ring of primordial initial cells within the periphery of the shoot apical meristem, a pool of organogenic stem cells that generates all of the organs of the plant shoot. At maturity, the grass leaf is a flattened, strap-like organ comprising a proximal supportive sheath surrounding the stem and a distal photosynthetic blade. The sheath and blade are partitioned by a hinge-like auricle and the ligule, a fringe of epidermally derived tissue that grows from the adaxial (top) leaf surface. Together, the ligule and auricle comprise morphological novelties that are specific to grass leaves. Understanding how the planar outgrowth of grass leaves and their adjoining ligules is genetically controlled can yield insight into their evolutionary origins. Here we use single-cell RNA-sequencing analyses to identify a ‘rim’ cell type present at the margins of maize leaf primordia. Cells in the leaf rim have a distinctive identity and share transcriptional signatures with proliferating ligule cells, suggesting that a shared developmental genetic programme patterns both leaves and ligules. Moreover, we show that rim function is regulated by genetically redundant Wuschel-like homeobox3 (WOX3) transcription factors. Higher-order mutations in maize Wox3 genes greatly reduce leaf width and disrupt ligule outgrowth and patterning. Together, these findings illustrate the generalizable use of a rim domain during planar growth of maize leaves and ligules, and suggest a parsimonious model for the homology of the grass ligule as a distal extension of the leaf sheath margin.

59 BASIC BIOLOGICAL SCIENCES↗

Bridging Nano- and Microscale X-Ray Tomography for Battery Research by Leveraging Artificial Intelligence

X-ray computed tomography (CT) is a non-destructive imaging technique in which contrast originates from the materials' absorption coefficient. The recent development of laboratory nanoscale CT (nano-CT) systems has pushed the spatial resolution for battery material imaging to voxel sizes of 50 nm, a limit previously achievable only with synchrotron facilities. Given the non-destructive nature of CT, in situ and operando studies have emerged as powerful methods to quantify morphological parameters, such as tortuosity factor, porosity, surface area and volume expansion, during battery operation or cycling. Combined with artificial intelligence and machine learning analysis techniques, nano-CT has enabled the development of predictive models to analyse the impact of the electrode microstructure on cell performances or the influence of material heterogeneities on electrochemical responses. In this Review, we discuss the role of X-ray CT and nano-CT experimentation in the battery field, discuss the incorporation of artificial intelligence and machine learning analyses and provide a perspective on how the combination of multiscale CT imaging techniques can expand the development of predictive multiscale battery behavioural models.

diagnostics↗