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At least 1,099 records · Page 61

Synthesis and Characterization of Pd-based Nanomaterials

Bimetallic nanoparticles (BNPs) consist of two different types of metals or alloys that are bonded together. Unique properties such as optical, electronic, thermal, and catalytic effects differ for each type of BNP. Important BNPs range from Au-Pd, Ag- Pt, Au-Pt, and Ag-Ni. Pd bimetallic nanoparticles are of interest due to their many applications such as catalysis and sensing. Bimetallic catalysts have increase reaction rates and have improved catalyst stability through the geometry and ligand distribution. Pd nanoparticles are considered to be a strong catalyst due to their high activity at low temperatures and high tolerance to moisture. The catalytic properties of bimetallic nanoparticles depend on the structural properties such as size and shape. Core-shell, hollow structure, and multi-shell alloy are three possible structures nanoparticles can form as bimetallic catalysts. BNPs can be synthesized through different methods to control the size, shape, and structure. To obtain different morphologies, a variety of methods can be performed. Different methods can range from the usage of the glancing angle deposition (GLAD) to the galvanic replacement reaction, but the methods all depend on the properties of the metals. The galvanic displacement reaction was the method used to obtain Pd-based nanoparticles. This reaction is best know for obtaining hollow shaped NPs. To determine what redox process was preformed, the activity series of metals was used. From the activity series of metals, silver (Ag) was selected to preform Pd-based nanoparticles. Objectives: Synthesize Ag nanoparticles and Ag-Pd nanoparticles to understand the morphology. Characterize the synthesized nanoparticles using scanning electron microscopy (SEM), phase analysis light scattering (PALS), dynamic light scattering (DLS), energy dispersive X-ray spectroscopy (EDS), and UV-Vis spectroscopy. Results: In the UV-Vis spectrum, the Ag-Pd bimetallic NP's plasmon band decreased as the volume of palladium increased. The surface charge increases as the concentration of palladium increases. The Pd{sup 2+} ions interact with the sodium citrate surface, and decrease the negative charge. Conclusion: Ag-Pd nanoparticles were successfully created and stabilized with sodium citrate. The addition of Pd decreased the prominent plasmon band of the Ag nanoparticles. The SEM analysis showed that Ag nanoparticles had a well-defined structure, while the Ag-Pd nanoparticles showed hollow and rough structure. The EDX analysis confirmed the presence of silver and palladium. This material can be used in many industrial and research fields such as organic synthesis, fuel cells, and environmental sensing and remediation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Achieving Stable Molybdenum Oxide Cathodes for Aqueous Zinc-Ion Batteries in Water-in-Salt Electrolyte

A layered MoO 3 material with large interlayer spacing represents a promising cathode for aqueous rechargeable Zn-ion batteries (ARZIBs), but the implementation of this material is limited due to the intrinsically low conductivity and poor structural stability. A 30 m ZnCl 2 water-in-salt electrolyte (WISE) was introduced to a MoO 3 nanobelt cathode for the first time, significantly increasing the stability of MoO 3 cathodes compared to those in 3 M ZnSO 4 and 3 M ZnCl2 electrolyte. The Zn/MoO 3 cell in WISE unambiguously demonstrated significantly improved rate performance delivering 349, 253, and 222 mAh/g at 100, 500, and 1000 mA/g, denoting a 2×, and 12× capacity increase of those achieved in 3 M electrolytes at 500 and 1000 mA/g, respectively. A capacity retention rate of 73% was achieved after (dis)charging at 100 mA/g for 100 cycles, and no obvious capacity fading was observed at higher current densities of 500 mA/g and 2A/g. A compilation of structural and morphological characterization was systematically performed to provide insight into the mechanisms of the improved performance in ZnCl 2 WISE for the MoO3 cathode materials. Specifically, our data collectively suggested that the drastic fading in 3M electrolytes can be attributed to the parasitic surface deposits on Zn originated from Mo dissolution and H 2 formation due to Zn corrosion and hydrogen evolution reaction (HER), which were significantly suppressed in the ZnCl 2 WISE. The direct visualization of these side reactions was achieved for the first time in the Zn-MoO 3 system, using an in situ optoelectrochemical measurement.

25 ENERGY STORAGE↗

Dynamic Motions of Topological Defects in Nematic Liquid Crystals under Spatial Confinement

Abstract Topological defects (TDs) have become a sensational topic due to their significant influence on the unusual optical and physiochemical characteristics of the material. To facilitate their application across a wide range of disciplines it is desirable to analyze and gain fundamental understanding of TDs in both equilibrium and nonequilibrium systems. Liquid crystals (LCs) are considered an ideal system for study given the direct visualization of TDs and a straightforward analyzation process. In addition to the equilibrium morphology of LC TDs, it is also of great interest to track and control the formation and annihilation of defects during thermodynamic processes. However, controlling the dynamic behavior of formed defects remains a challenge. Here, nematic LCs confined in a cell exhibiting surfaces with periodic anchoring conditions containing surface topography are relied on. The effects of patterned surface characteristics such as width, periodicity, and degree of curvature on defects dynamic motion, stabilization, and annihilation are explored. The computational experiments recapitulate the TDs transition path and provide free energy‐based predictions of critical distances for defect annihilation. Taken together, this simple approach offers a promising opportunity to control the dynamics of TDs in LCs through chemical patterned surfaces with topography.

36 MATERIALS SCIENCE↗

Composite coatings from polycarbosilane derived SiC and Al/SiC cermet active fillers as protective barriers against steel corrosion

Stainless steel is used throughout the world as a structural material. However, it undergoes corrosion damage when exposed to extremely corrosive media, such as the marine environment. An alternative to solve this problem lies in the development of coatings that can withstand extreme conditions but also be easily deposited with inherently corrosion-resistant materials such as silicon carbide (SiC). The present study shows a simple method to produce Al/SiC cermet powders by attrition milling. The resulting cermet powders with a metallic matrix and hemispherical morphology, were employed as fillers in polycarbosilane (PCS) solutions that were sprayed on A304 stainless steel substrates. Al/SiC composite coatings were produced after heating the sprayed suspensions at 700 °C for 1 h in Ar atmosphere. The resulting composite coatings exhibited low surface energies (< 35 mN/m), water contact angles of 53°, and adhesion strength of up to 30 MPa. Finally, corrosion tests were performed in a cyclic corrosion test chamber, showing that these coatings effectively reduced the corrosion rate of stainless steel by 87%, reaching corrosion rate values of 0.007 g/cm 2 year.

36 MATERIALS SCIENCE↗

Structural Transformation and Degradation of Cu Oxide Nanocatalysts during Electrochemical CO 2 Reduction

The electrochemical CO 2 reduction reaction (CO 2 RR) holds enormous potential as a carbon-neutral route to the sustainable production of fuels and platform chemicals. The durability for long-term operation is currently inadequate for commercialization, however, and the underlying deactivation process remains elusive. A fundamental understanding of the degradation mechanism of electrocatalysts, which can dictate the overall device performance, is needed. In this work, we report the structural dynamics and degradation pathway of Cu oxide nanoparticles (CuO x NPs) during the CO 2 RR by using in situ small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS). The in situ SAXS reveals a reduction in the size of NPs when subjected to a potential at which no reaction products are detected. At potentials where the CO 2 RR starts to occur, CuO x NPs are agglomerated through a particle migration and coalescence process in the early stage of the reaction, followed by Ostwald ripening (OR) as the dominant degradation mechanism for the remainder of the reaction. As the applied potential becomes more negative, the OR process becomes more dominant, and for the most negative applied potential, OR dominates for the entire reaction time. The morphological changes are linked to a gradual decrease in the formation rate for multicarbon products (C 2 H 4 and ethanol). Other reaction parameters, including reaction intermediates and local high pH, induce changes in the agglomeration process and final morphology of the CuO x NPs electrode, supported by post-mortem ex situ microscopic analysis. The in situ XAS analysis suggests that the CuO x NPs reduced into the metallic state before the structural transformation was observed. The introduction of high surface area carbon supports with ionomer coating mitigates the degree of structural transformation and detachment of the CuO x NPs electrode. These findings show the dynamic nature of Cu nanocatalysts during the CO 2 RR and can serve as a rational guideline toward a stable catalyst system under electrochemical conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thin Film Characterization on Cu/SnAg Solder Interface for 3D Packaging Technologies

Copper is a commonly used interconnect metal in microelectronic interconnects due to its exceptional electrical and thermal properties. Particularly in applications of the 2.5 and 3D integration, Cu is utilized in through-silicon-vias (TSVs) and flip chip interconnects between microelectronic chips for providing miniaturization, lower power and higher performance than current 2D packaging approaches. Furthermore, SnAg capped Cu pillars are a common high-density interconnect technology for flip chip bonding. For these interconnects, specific properties of the Cu surface, such as roughness and cleanliness, are an important factor in the process to ensure quality solder bumps. During electroplating, tight processing parameters must be met so that defects are avoided, and high bump uniformity is achieved. An understanding of the interactions at the solder and Cu pillar interface is needed, based on the electroplating parameters, to determine the best method for populating solder on the wafer surface. In this study, surface treatment techniques such as oxygen plasma cleaning were performed on the Cu surfaces and the SnAg plating chemistry for depositing the solder were evaluated through hull cell testing to qualitatively determine the range of current densities to investigate. It was observed that current density while plating played a large role in solder bump deposition morphology. At the higher current densities greater than 60 mA/cm 2 , bump height non-uniformity and dendritic growth are observed and at lower current densities, less than or equal to 60 mA/cm 2 , uniform, continuous bump height occurred.

36 MATERIALS SCIENCE↗

Enhancing Electrochemical CO2 Conversion by Controlling Electrocatalysts' Structure

Electrochemical reduction of CO2 (CO2R) to valuable, carbon-neutral chemical feedstocks and storable fuels driven by renewable electricity has been recognized as one of the promising pathways to mitigate the greenhouse effect, reduce global demand for fossil fuels, achieve carbon neutrality, and create sustainable energy. Tremendous ongoing efforts have focused on controlling the morphology, composition, structure, size, defects, etc., of the electrocatalysts to improve product selectivity, activity, and durability to approach the feasibility of practical applications (current density higher than 200 mA/cm2 and lifetime ~1,000 hr+). This presentation will discuss how the geometry and surface composition of novel copper- and tin-based catalysts would maximize the CO2 conversion to carbon monoxide and liquid formic acid/formate in both common aqueous H-cell and electrolyzer configurations. Several spectroscopic, microscopic, and electrochemical characterization tools have been utilized to correlate the changes in the structural, physico-chemical, and electronic properties with the catalytic activity. Our work provides additional electrocatalyst design considerations for high-performance CO2 electrolysis.

Nguyen Phan, Thuy Duong↗

Ultrastable Gold Nanostars via Bottlebrush-like Block Copolymers

Gold (Au) nanostars are plasmonic nanostructures possessing potentials for small molecule detection, photocatalytic activities, and photothermal therapy. However, Au nanostars synthesized in the traditional way are often plagued by poor photo, thermal, and chemical stabilities. Here, we report an unconventional route to the synthesis of ultrastable colloidal Au nanostars enabled by bottlebrush-like block copolymers (BBCPs), dispensing with the need for Au seeds. Crafting of Au nanostars using BBCPs is rendered by bridging the latter with Au 3+ ions as cross-linkers that have multiple coordination sites. Notably, the presence of a covalently tethered polymer shell on the surface of Au nanostars (i.e., polymer-ligated Au nanostars) imparts remarkably high stability under high temperature and laser excitation over conventional cetyltrimethylammonium bromide (CTAB)-mediated Au nanostars. Due to enhanced laser stability, plasmonic fields near Au nanostars can be visualized under high laser fluence by ultrafast electron microscopy (UEM) without morphological degradation. Notably, the presence of insulating polystyrene chains does not compromise the plasmonic field distribution, with the highest field intensity observed along the star arms. In conclusion, the greatly improved long-term photo, thermal, and chemical stabilities make Au nanostars a prospective noble metal nanomaterial for a range of sensing applications.

Cellulose↗

W-induced morphological modification of NiFe layered double hydroxides as efficient electrocatalysts for overall water splitting

Layered double hydroxides (LDHs) are one of the most efficient electrocatalysts for water splitting due to their nanosheet features and compositional flexibilities. This work explored the impact of W precursor concentration (0 ~ 10 mM) on LDH morphologies and performance in hydrogen production. Using an electrodeposition W-doping process, W-induced NiFe LDHs (NiFeW-LDHs) were in-situ grown on carbon fiber papers for water splitting. A performance peak was found at a W doping of 5 mM with well-aligned nanosheets, which not only boosted the charge transfer ability and gas evolution but also offered more than a four-fold electrochemical surface area increase compared to film-like NiFe hydroxides. The NiFeW-LDHs exhibited remarkable performance compared to NiFe hydroxides, showing decreased overpotentials of 31 mV and 114 mV for the oxygen evolution reactions (OERs) and hydrogen evolution reactions (HERs) at 10 mA/cm 2 and -10 mA/cm 2 , respectively, in alkaline media. The performance enhancement at 5 mM W-doping was linked to the well-aligned NiFeW-LDH nanosheets; smaller, less-textured nanosheets were observed with lower or higher W precursor concentrations (2.5 mM or >7.5 mM), leading to inferior OER and HER performances. Hence, an appropriate W doping is crucial to generating the morphologies that contribute to the higher performance of NiFeW-LDHs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electron microscopy characterization of the fuel-cladding interaction in medium burnup annular fast reactor MOX

In this work, we present electron microscopy data focused on the fuel-cladding interaction layer in annular fast reactor MOX with HT-9 cladding at medium burnup. In agreement with previous literature data, the volatile fission products Cs, Te and I have migrated radially into the extreme fuel periphery and partially interacted with the cladding. The accumulation of Cs has occurred in the outermost rim of the fuel pellet, where grain recrystallization has also been observed. Significant amounts of Pd have been found in the interaction zone, particularly in the sample taken from the upper half of the fissile column where the cladding temperatures are higher. At this axial location, Cr has been enriched at the cladding inner surface and diffused into the fuel. Furthermore, chromium remains mainly in metallic form, but locally formed oxides. The fission products Cs, Te and I are found, with variable composition, in form of nanocrystalline regions dispersed in the metallic Cr-rich layer. The morphology and chemical characteristics of the layer suggest a non-oxidative corrosion mechanism as principal cladding degradation phenomenon occurring in this sample, with local onset of Cr oxidation within the nanocrystalline precipitates.

36 MATERIALS SCIENCE↗

Reconstruction and Dissolution of Copper Catalysts during Electrocatalytic Nitrate Reduction

Copper-based electrocatalysts are widely explored for electrochemical nitrate remediation, yet their stability under operating conditions remains poorly understood. While nanoscale and subnanoscale Cu motifs are known to restructure during the nitrate reduction reaction (NO 3 RR), how these transformations translate into irreversible material loss remains unclear. Here, we quantify Cu dissolution during NO 3 RR as a function of catalyst architecture and electrolyte chemistry using two model systems: single-atom Cu (Cu 1 ) and Cu nanoparticles (Cu NP ). Time-resolved leaching measurements, integrated with in situ X-ray absorption spectroscopy (XAS), reveal measurable Cu loss for both catalysts during NO 3 RR. Dissolution is concentrated at the initiation of electrolysis, coinciding with rapid restructuring, and depends strongly on morphology, with Cu NP consistently exhibiting greater Cu loss than Cu 1 . In situ XAS reveals that Cu 1 forms transient metallic clusters under reduction that largely redisperse upon returning to open-circuit voltage, whereas Cu NP undergoes reduction of an oxidized surface layer accompanied by sustained Cu loss during electrolysis. Notably, the presence of nitrate significantly intensifies restructuring and Cu loss, highlighting the critical role of electrolyte composition. Furthermore, these findings establish a direct link between electrochemical restructuring and Cu dissolution, unveiling electrolyte-dependent interactions as key determinants of catalyst durability in electrochemical nitrate conversion.

36 MATERIALS SCIENCE↗

Light absorption enhancement of black carbon in a pyrocumulonimbus cloud

Abstract Pyrocumulonimbus (pyroCb) firestorm systems have been shown to inject significant amounts of black carbon (BC) to the stratosphere with a residence time of several months. Injected BC warms the local stratospheric air, consequently perturbing transport and hence spatial distributions of ozone and water vapor. A distinguishing feature of BC-containing particles residing within pyroCb smoke is their thick surface coatings made of condensed organic matter. When coated with non-refractory materials, BC’s absorption is enhanced, yet the absorption enhancement factor ( E abs ) for pyroCb BC is not well constrained. Here, we perform particle-scale measurements of BC mass, morphology, and coating thickness from inside a pyroCb cloud and quantify E abs using an established particle-resolved BC optics model. We find that the population-averaged E abs for BC asymptotes to 2.0 with increasing coating thickness. This value denotes the upper limit of E abs for thickly coated BC in the atmosphere. Our results provide observationally constrained parameterizations of BC absorption for improved radiative transfer calculations of pyroCb events.

54 ENVIRONMENTAL SCIENCES↗

Biopolymer Modified Cementitious Systems with Radically Superior Strength and Durability

This project was a pioneering study of the effect of nanochitin additives on setting time, rheological, and mechanical properties of cementitious materials. Chitin is the second most abundant biopolymer in nature after cellulose and is readily available from byproducts of the growing seafood industry. In this study, chitin powder from shrimp shells was processed into chitin nanocrystals (ChNCs) and chitin nanofibers (ChNFs). Ch-Cs delayed initial and final set times with their high ionic surface charges likely by electrostatic repulsion. The viscosity of fresh cement paste increased with Ch-NFs, while Ch-NCs did not significantly affect rheological properties. The distinct effects of the two nanochitin forms are attributed to the mobility of the different morphologies of the rod-like ChNCs vs. the entangled and restrained network of the ChNFs. Nanochitin forms showed encouraging results by significantly increasing flexural strength by ~40% at the optimum concentration of 0.05 wt% and significant increases in fracture energy. These bio-additives were found promising and future studies should continue to evaluate their use in concrete.

36 MATERIALS SCIENCE↗

Single-Cell RNA-Seq Reveals Transcriptomic Heterogeneity and Post-Traumatic Osteoarthritis-Associated Early Molecular Changes in Mouse Articular Chondrocytes

Articular cartilage is a connective tissue lining the surfaces of synovial joints. When the cartilage severely wears down, it leads to osteoarthritis (OA), a debilitating disease that affects millions of people globally. The articular cartilage is composed of a dense extracellular matrix (ECM) with a sparse distribution of chondrocytes with varying morphology and potentially different functions. Elucidating the molecular and functional profiles of various chondrocyte subtypes and understanding the interplay between these chondrocyte subtypes and other cell types in the joint will greatly expand our understanding of joint biology and OA pathology. Although recent advances in high-throughput OMICS technologies have enabled molecular-level characterization of tissues and organs at an unprecedented resolution, thorough molecular profiling of articular chondrocytes has not yet been undertaken, which may be in part due to the technical difficulties in isolating chondrocytes from dense cartilage ECM. In this study, we profiled articular cartilage from healthy and injured mouse knee joints at a single-cell resolution and identified nine chondrocyte subtypes with distinct molecular profiles and injury-induced early molecular changes in these chondrocytes. We also compared mouse chondrocyte subpopulations to human chondrocytes and evaluated the extent of molecular similarity between mice and humans. This work expands our view of chondrocyte heterogeneity and rapid molecular changes in chondrocyte populations in response to joint trauma and highlights potential mechanisms that trigger cartilage degeneration.

59 BASIC BIOLOGICAL SCIENCES↗

Glancing Angle Deposition in Gas Sensing: Bridging Morphological Innovations and Sensor Performances

Glancing Angle Deposition (GLAD) has emerged as a versatile and powerful nanofabrication technique for developing next-generation gas sensors by enabling precise control over nanostructure geometry, porosity, and material composition. Through dynamic substrate tilting and rotation, GLAD facilitates the fabrication of highly porous, anisotropic nanostructures, such as aligned, tilted, zigzag, helical, and multilayered nanorods, with tunable surface area and diffusion pathways optimized for gas detection. This review provides a comprehensive synthesis of recent advances in GLAD-based gas sensor design, focusing on how structural engineering and material integration converge to enhance sensor performance. Key materials strategies include the construction of heterojunctions and core–shell architectures, controlled doping, and nanoparticle decoration using noble metals or metal oxides to amplify charge transfer, catalytic activity, and redox responsiveness. GLAD-fabricated nanostructures have been effectively deployed across multiple gas sensing modalities, including resistive, capacitive, piezoelectric, and optical platforms, where their high aspect ratios, tailored porosity, and defect-rich surfaces facilitate enhanced gas adsorption kinetics and efficient signal transduction. These devices exhibit high sensitivity and selectivity toward a range of analytes, including NO2, CO, H2S, and volatile organic compounds (VOCs), with detection limits often reaching the parts-per-billion level. Emerging innovations, such as photo-assisted sensing and integration with artificial intelligence for data analysis and pattern recognition, further extend the capabilities of GLAD-based systems for multifunctional, real-time, and adaptive sensing. Finally, current challenges and future research directions are discussed, emphasizing the promise of GLAD as a scalable platform for next-generation gas sensing technologies.

Chemistry↗

The stellar mass Fundamental Plane: the virial relation and a very thin plane for slow rotators

ABSTRACT Early-type galaxies – slow and fast rotating ellipticals (E-SRs and E-FRs) and S0s/lenticulars – define a Fundamental Plane (FP) in the space of half-light radius Re, enclosed surface brightness Ie, and velocity dispersion σe. Since Ie and σe are distance-independent measurements, the thickness of the FP is often expressed in terms of the accuracy with which Ie and σe can be used to estimate sizes Re. We show that: (1) The thickness of the FP depends strongly on morphology. If the sample only includes E-SRs, then the observed scatter in Re is $\sim 16{{\ \rm per\ cent}}$, of which only $\sim 9{{\ \rm per\ cent}}$ is intrinsic. Removing galaxies with M* < 1011 M⊙ further reduces the observed scatter to $\sim 13{{\ \rm per\ cent}}$ ($\sim 4{{\ \rm per\ cent}}$ intrinsic). The observed scatter increases to $\sim 25{{\ \rm per\ cent}}$ usually quoted in the literature if E-FRs and S0s are added. If the FP is defined using the eigenvectors of the covariance matrix of the observables, then the E-SRs again define an exceptionally thin FP, with intrinsic scatter of only 5 per cent orthogonal to the plane. (2) The structure within the FP is most easily understood as arising from the fact that Ie and σe are nearly independent, whereas the Re−Ie and Re−σe correlations are nearly equal and opposite. (3) If the coefficients of the FP differ from those associated with the virial theorem the plane is said to be ‘tilted’. If we multiply Ie by the global stellar mass-to-light ratio M*/L and we account for non-homology across the population by using Sérsic photometry, then the resulting stellar mass FP is less tilted. Accounting self-consistently for M*/L gradients will change the tilt. The tilt we currently see suggests that the efficiency of turning baryons into stars increases and/or the dark matter fraction decreases as stellar surface brightness increases.

Bernardi, M.↗

Nanoscale cooperative adsorption for materials control

Abstract Adsorption plays vital roles in many processes including catalysis, sensing, and nanomaterials design. However, quantifying molecular adsorption, especially at the nanoscale, is challenging, hindering the exploration of its utilization on nanomaterials that possess heterogeneity across different length scales. Here we map the adsorption of nonfluorescent small molecule/ion and polymer ligands on gold nanoparticles of various morphologies in situ under ambient solution conditions, in which these ligands are critical for the particles’ physiochemical properties. We differentiate at nanometer resolution their adsorption affinities among different sites on the same nanoparticle and uncover positive/negative adsorption cooperativity, both essential for understanding adsorbate-surface interactions. Considering the surface density of adsorbed ligands, we further discover crossover behaviors of ligand adsorption between different particle facets, leading to a strategy and its implementation in facet-controlled synthesis of colloidal metal nanoparticles by merely tuning the concentration of a single ligand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗