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At least 667 records · Page 37

Morphology Dependent Reactivity of CsO $x$ Nanostructures on Au(111): Binding and Hydrogenation of CO 2 to HCOOH

Cesium oxide (CsO $x$ ) nanostructures grown on Au(111) behave as active centers for CO 2 binding and hydrogenation reactions. The morphology and reactivity of these CsO $x$ systems were investigated as a function of alkali coverage using scanning tunnelling microscopy (STM), ambient pressure X-ray photoelectron spectroscopy (AP-XPS), and density functional theory (DFT) calculations. STM results show that initially (0.05 - 0.10 ML) cesium oxide clusters (Cs 2 O 2 ) grow at the elbow sites of the herringbone of Au(111), subsequently transforming into two-dimensional islands with increasing cesium coverage (> 0.15 ML). XPS measurements reveal the presence of suboxidic (Cs $y$ O; $y$ ≥ 2) species for the island structures. The higher coverages of cesium oxide nanostructures contain a lower O/Cs ratio resulting in a stronger binding of CO 2 . Moreover, the O atoms in the Cs $y$ O structure undergo a rearrangement upon the adsorption of CO 2 which is a reversible phenomenon. Under CO 2 hydrogenation conditions, the small Cs 2 O 2 clusters are hydroxylated, thereby preventing the adsorption of CO 2 . However, the hydroxylation of the higher coverages of Cs $y$ O did not prevent CO 2 adsorption, and the adsorbed CO 2 transformed to HCOO species that eventually yield HCOOH. DFT calculations further confirm that the dissociated H 2 attacks the C in the adsorbate to produce formate, which is both thermodynamically and kinetically favored during the CO 2 reaction with hydroxylated Cs $y$ O. These results demonstrate that cesium oxide by itself is an excellent catalyst for CO 2 hydrogenation that could produce formate, an important intermediate for the generation of value-added species. The role of the alkali oxide nanostructures as active centers, not merely as promoters, may have broad implications wherein the alkali oxides can be considered in the design of materials tuned for specific applications in heterogeneous catalysis.

03 NATURAL GAS↗

Automated Gold Nanorod Spectral Morphology Analysis Pipeline

The development of a colloidal synthesis procedure to produce nanomaterials with high shape and size purity is often a time-consuming, iterative process. This is often due to quantitative uncertainties in the required reaction conditions and the time, resources, and expertise intensive characterization methods required for quantitative determination of nanomaterial size and shape. Absorption spectroscopy is often the easiest method for colloidal nanomaterial characterization. However, due to the lack of a reliable method to extract nanoparticle shapes from absorption spectroscopy, it is generally treated as a more qualitative measure for metal nanoparticles. This work demonstrates a gold nanorod (AuNR) spectral morphology analysis tool, called AuNR-SMA, which is a fast and accurate method to extract quantitative structural information from colloidal AuNR absorption spectra. To demonstrate the practical utility of this model, we apply it to three distinct applications. First, we demonstrate this model's utility as an automated analysis tool in a high-throughput AuNR synthesis procedure by generating quantitative size information from optical spectra. Second, we use the predictions generated by this model to train a machine learning model to predict the resulting AuNR size distributions under specified reaction conditions. Third, we apply this model to spectra extracted from the literature where no size distributions are reported and impute unreported quantitative information on AuNR synthesis. This approach can potentially be extended to any other nanocrystal system where absorption spectra are size dependent, and accurate numerical simulation of absorption spectra is possible. In addition, this pipeline could be integrated into automated synthesis apparatuses to provide interpretable data from simple measurements, help explore the synthesis science of nanoparticles in a rational manner, or facilitate closed-loop workflows.

36 MATERIALS SCIENCE↗

The Effects of Morphology and Hydration on Anion Transport in Self-Assembled Nanoporous Membranes

Ordered nanoporous polymer membranes offer opportunities for systematically probing the mechanisms of ion transport under confinement and for realizing useful materials for electrochemical devices. Here, we examine the impact of morphology and ion hydration on the transport of hydroxide and bromide anions in nanostructured polymer membranes with 1 nm scale pores. We use aqueous lyotropic self-assembly of an amphiphilic monomer, with a polymerizable surfactant to create direct hexagonal (H I ) and gyroid mesophases. UV-induced cross-linking leads to the formation of nanoporous polymers with water continuous channels. The membranes are mechanically robust and chemically durable, resisting degradation during extended exposure to 1 M NaOH solutions. We use a combination of electrochemical impedance spectroscopy, pulsed-field gradient NMR spectroscopy, and molecular simulations to elucidate anion and water transport. The as-prepared hexagonal systems display higher conductivity and lower activation energies for both anions relative to the gyroid system. When compared at equivalent hydration, however, gyroid and hexagonal membranes show similar activation energies, with nearly identical conductivities at ambient temperatures. Both ionic conductivity and water diffusivity increase with increasing hydration. Here, the water uptake as a function of relative humidity for the hexagonal and gyroid mesophases ultimately dictates the water diffusion and magnitude of the ionic conductivity, with the hexagonal system showing overall higher capacity for hydration and thus faster ion transport. The durability of these materials under aggressive alkaline conditions and their relatively high hydroxide ion conductivity suggest that these nanostructured polymers could be of interest as membranes for alkaline fuel cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Subdiffraction Imaging of Carrier Dynamics in Halide Perovskite Semiconductors: Effects of Passivation, Morphology, and Ion Motion

In this article, we spatially resolve photocarrier dynamics in halide perovskites using time-resolved electrostatic force microscopy (trEFM) to map surface potential equilibration during photoexcitation. We present a unified interpretation of trEFM, which measures the evolution of the surface potential in response to photoexcitation. We show that trEFM measurements correlate with surface recombination velocity and carrier lifetimes, validated with time-resolved photoluminescence imaging. We further validate the interpretation of trEFM through wavelength- and intensity-dependent measurements and with drift-diffusion simulations. We compare several passivation agents, including (3-aminopropyl)trimethoxysilane (APTMS), [3-(2-aminoethylamino)propyl]trimethoxysilane (AEAPTMS), and phenethylammonium iodide (PEAI). The results reveal heterogeneity in surface potential equilibration times that correlates with perovskite film morphology and nanoscale variations in recombination dynamics following surface passivation. Not only do our results highlight the potential for further improvement of passivation strategies, but also the necessity of high spatial and temporal resolution methods, like trEFM, to evaluate next-generation semiconductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave-Based Synthesis of Functional Morphological Variants and Carbon Nanotube-Based Composites of VS 4 for Electrochemical Applications

A novel facile, fast, and efficient microwave-assisted method was developed to synthesize a number of diverse nanostructured motifs (ranging from nanorods to nanoflowers) of VS 4 along with its associated composite heterostructures, VS 4 /multi-walled carbon nanotube (MWNT; i.e., multi-walled carbon nanotubes). Specifically, we have probed and correlated the effects of a number of specific experimental variables, including primarily precursor, solvent, temperature, and time. We noted that nanorods formed more readily with VO(acac) 2 as the vanadium precursor and n-methyl-2-pyrrolidone (NMP) as a polar reaction solvent. By contrast, we determined that hierarchical three-dimensional (3D) nanoflower-like assemblies, ranging in size from 100 to 200 nm in average diameter, could be controllably synthesized by using Na 3 VO 4 as the vanadium precursor and an aqueous water: polar solvent mixture as the reaction medium. We also observed that VS 4 disintegrates, when in the presence of either air, solution, or a combination of these environments, and established that the extent of VS4 nanorod decomposition could be almost fully prevented by storage under nitrogen. From an application’s perspective, our VS 4 is electrochemically active and shows behavior, consistent with the literature. In particular, as compared with pristine VS 4 nanorods alone, we observed enhanced electrochemical activity with (i) 3D hierarchical flower-like motifs, (ii) unique necklace-like VS 4 nanorod–MWNT composites, and (iii) samples in which as-prepared VS4 nanorods had been annealed. Moreover, we found that the rational application of specific physical and chemical processing treatments, such as (i) thermal annealing to improve crystallinity, (ii) the addition of MWNTs to form conductive composites, and (iii) the evolution of morphology from one-dimensional (1D) nanorods to more complex 3D nanoflowers, was favorable to the resulting electrochemical performance with respect to increasing stability and reversibility.

25 ENERGY STORAGE↗

Unveiling the Origin of Morphological Instability in Topologically Complex Electrocatalytic Nanostructures

Coarsening and degradation phenomena in metals have largely focused on thermally driven processes, such as bulk and surface diffusion. However, dramatic coarsening has been reported in high-surface-area, nanometer-sized Pt-based catalysts during potential cycling in an electrolyte at room temperature─a temperature too low for the process to be explained purely by surface mobility values measured in both vacuum and electrolytes (∼10 –22 and ∼10 –18 cm 2 /s, respectively). This morphological evolution must be due to a different mechanism for mass transport that is sensitive to electrochemical conditions (e.g., electrolyte composition, potential limits, and scan rate). However, there have been no notable studies of electrochemically induced coarsening in nanometer-sized electrocatalysts. Here, we unveil the origins of coarsening in an electrolyte through coupled in situ experiments and atomistic kinetic Monte Carlo (kMC) simulations. Our work demonstrates electrochemical coarsening is driven by two concurrent mechanisms that can be explained at the atomistic level: (i) dissolution/redeposition during the reduction of an oxidized species and (ii) rapid surface diffusion of undercoordinated atoms.

gold↗

Strained-Induced Morphological Reconstruction of RuO 2 (110) Thin-Film Electrocatalysts

Strain is a widely used strategy for electrocatalyst engineering. Overstraining, however, can lead to unintentional materials transformation. We investigate the impact of strain on the surface morphology of a rutile RuO 2 (110) film grown on a symmetry-matching rutile TiO 2 (110) substrate. When the film thickness exceeds 9 nm, the RuO 2 surface relaxes by forming step edges that expose the {011} plane. Density functional theory (DFT) calculation shows that the (011) facet is among the lower energy surfaces of rutile RuO 2 , suggesting that this formation incurs minimal energetic penalties. In situ atomic force microscopy (AFM) shows that the film maintains the (110) structure of the terrace during electrochemistry. Inductively coupled plasma–mass spectrometry (ICP-MS) further reveals the insensitivity of the Ru dissolution to strain. Here, our findings show a strain-relieving pathway via surface reconstruction in RuO 2 (110) and provide an example of a strain-relieving mechanism that does not affect dissolution.

Evolution reactions↗

Effect of Sulfonation Level on the Percolated Morphology and Proton Conductivity of Hydrated Fluorine-Free Copolymers: Experiments and Simulations

Using all-atom molecular dynamics simulations and a variety of experimental methods, we previously reported on a linear polyethylene with pendant phenyl sulfonated groups precisely on every fifth carbon along the backbone. With increasing relative humidity this fluorine-free polymer self-assembled to form nanoscale water channels and exhibited exceptional proton conductivity. Expanding upon those findings, here we explore partially sulfonated random copolymers, referred to as p 5PhSH-Y. Using either acetyl sulfate or sulfuric acid, a wide range of sulfonation levels were prepared ( Y = 34−98%) corresponding to ion-exchange capacities (IEC) of 2.0−4.4 mmol/g. Combining experimental techniques and all-atom molecular dynamics simulations, we study the effect of Y on water uptake, nanoscale morphology, and the proton/water transport properties of p5PhSH- Y . The proton conductivity of p 5PhSH- Y increases with relative humidity and with Y and achieves values in excess of 0.1 S/cm. These high conductivities are attributed to high IEC and welldeveloped nanoscale percolated hydrophilic domains made possible by the flexible backbone. We quantitatively describe the nature of the water channels using the characteristic distance, channel width distribution, the area per sulfonate group at the hydrophilic/ hydrophobic interface, and the fractal dimension. Notably, the channel widths and the areas per sulfonate group are nominally independent of the level of sulfonation, while depending significantly on the level of hydration. The fractal dimension of the water channels correlates strongly with the water diffusion coefficients calculated from the molecular dynamics (MD) simulations. These findings demonstrate that the p 5PhSH- Y hydrocarbon copolymers can be modified to tune properties, particularly proton conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cloud Morphology Evolution in Arctic Cold‐Air Outbreak: Two Cases During COMBLE Period

Abstract Cloud feedbacks play an important role in Arctic warming. Cloud morphology, for example, cloud size and spatial distributions, is among key factors that directly impact their radiative effects. In this work, we use two cases observed during the Cold‐air Outbreak (CAO) in the Marine Boundary Layer Experiment (COMBLE) to study the evolution of cloud size distributions as an air mass is advected from the Arctic over a comparatively warm ocean and cloud mesoscale organization changes from rolls to cells. Cloud objects are identified from Moderate Resolution Imaging Spectroradiometer (MODIS) reflectance images through an object segmentation procedure and roll breakup is identified by homogeneities in cloud water path (CWP). Roll breakup is found to be accompanied by a local minimum in wind shear and local maxima in cloud size and marine cold air outbreak index. The mean cloud horizontal aspect ratio has weak fetch dependency and is around 2 in roll, transition, and cell regimes. Regardless of distance from the ice edge, smaller clouds (<10 km 2 ) dominate the population number but not cloud cover. Cloud size distributions show bimodality in transition and cell regimes. For clouds with comparable sizes, mean nearest neighbor distances normalized by equivalent cloud radius converge to a single value for all regimes and for all but the smallest clouds, suggesting that clouds of comparable sizes in CAOs are separated by distance proportional to their sizes. The presented statistical results pave the way to evaluating model simulated cloud organizations during CAO events.

54 ENVIRONMENTAL SCIENCES↗

Overview of the Morphology and Chemistry of Diagenetic Features in the Clay-Rich Glen Torridon Unit of Gale Crater, Mars

The clay-rich Glen Torridon region of Gale crater, Mars, was explored between sols 2300 and 3007. Here, we analyzed the diagenetic features observed by Curiosity, including veins, cements, nodules, and nodular bedrock, using the ChemCam, Mastcam, and Mars Hand Lens Imager instruments. We discovered many diagenetic features in Glen Torridon, including dark-toned iron- and manganese-rich veins, magnesium- and fluorine-rich linear features, Ca-sulfate cemented bedrock, manganese-rich nodules, and iron-rich strata. We have characterized the chemistry and morphology of these features, which are most widespread in the higher stratigraphic members in Glen Torridon, and exhibit a wide range of chemistries. These discoveries are strong evidence for multiple generations of fluids from multiple chemical endmembers that likely underwent redox reactions to form some of these features. In a few cases, we may be able to use mineralogy and chemistry to constrain formation conditions of the diagenetic features. For example, the dark-toned veins likely formed in warmer, highly alkaline, and highly reducing conditions, while manganese-rich nodules likely formed in oxidizing and circumneutral conditions. We also hypothesize that an initial enrichment of soluble elements, including fluorine, occurred during hydrothermal alteration early in Gale crater history to account for elemental enrichment in nodules and veins. The presence of redox-active elements, including Fe and Mn, and elements required for life, including P and S, in these fluids is strong evidence for habitability of Gale crater groundwater. Hydrothermal alteration also has interesting implications for prebiotic chemistry during the earliest stages of the crater’s evolution and early Mars.

58 GEOSCIENCES↗

Transition Zone Morphology Dynamics of Dissolved Oxygen (DO) in a Salinity-Impacted Hyporheic Zone

Freshwater salinization is a common yet underappreciated environmental problem in rivers, yet how this process impacts the transport of dissolved oxygen (DO) in the hyporheic zone remains unknown. Here, using flume experiments and numerical simulations, we have demonstrated that the morphological dynamics of the DO transition zone are controlled by the dimensionless number Da·Ra –2 , a measure of the rate of aerobic respiration to free convection. At low Da·Ra –2 , the oxic front breaks up into fingers which subsequently grow, and leads to accelerating of DO transport and shrinking of the anaerobic zone in the underlying sediment. As Da·Ra –2 increases, the growth rate of the instability decreases, and the DO plume fingers are suppressed and delayed compared with the saltwater-freshwater interface, the mixing area between saltwater and freshwater. These results indicate that the freshwater salinization syndrome can have significant impacts on the functioning of aquifer ecosystems unless regulated and managed effectively.

54 ENVIRONMENTAL SCIENCES↗

Polymerized small molecular acceptor based all-polymer solar cells with an efficiency of 16.16% via tuning polymer blend morphology by molecular design

All-polymer solar cells (all-PSCs) based on polymerized small molecular acceptors (PSMAs) have made significant progress recently. Here, we synthesize two A-DA’D-A small molecule acceptor based PSMAs of PS-Se with benzo[c][1,2,5]thiadiazole A’-core and PN-Se with benzotriazole A’-core, for the studies of the effect of molecular structure on the photovoltaic performance of the PSMAs. The two PSMAs possess broad absorption with PN-Se showing more red-shifted absorption than PS-Se and suitable electronic energy levels for the application as polymer acceptors in the all-PSCs with PBDB-T as polymer donor. Cryogenic transmission electron microscopy visualizes the aggregation behavior of the PBDB-T donor and the PSMA in their solutions. In addition, a bicontinuous-interpenetrating network in the PBDB-T:PN-Se blend film with aggregation size of 10~20 nm is clearly observed by the photoinduced force microscopy. The desirable morphology of the PBDB-T:PN-Se active layer leads its all-PSC showing higher power conversion efficiency of 16.16%.

14 SOLAR ENERGY↗

Morphological and nanomechanical changes in tungsten in high heat flux conditions

Abstract Morphological and nanomechanical alteration of tungsten in extreme environments, like those in edge localized modes in nuclear fusion environments, up to 46.3 GWm −2 heat fluxes were experimentally simulated using electrothermal plasma. Surface and subsurface damage to the tungsten is seen mainly in the form of pore formation, cracks, and resolidified melt instabilities. Mirco voids, rosette-type microfeatures, core-shell structure, particle enrichment, and submicron channels all manifest in the damaged subsurface. The formation of voids in the subsurface was determined to originate from the ductile fracture of hot tungsten by plastic flow but not developed to cracking. The voids were preferentially settled in grain boundaries, interfaces. The directionality of elongated voids and grains is biased to the heat flow vector or plasma pathway, which is the likely consequence of the thermally driven grain growth and sliding in the high-temperature conditions. The presence of a border between the transient layer and heat-affected zone is observed and attributed to plasma shock and thermal spallation of fractural tungsten at high temperature. Plasma peening-like hardening effects in tungsten were observed in the range of 22.7–46.3 GWm −2 but least in the case of the lowest heat flux, 12.5 GWm −2 .

36 MATERIALS SCIENCE↗

The evolution of pit morphology and growth kinetics in aluminum during atmospheric corrosion

Abstract Assessing the lifetimes of alloys in humid, corrosive environments requires growth kinetic information regarding individual instances of damage, e.g. pit growth rates. Corrosion rates measured at the continuum scale using mass change convolute the rate of pit nucleation and growth, providing limited information on local kinetics. The current study used in-situ X-ray computed tomography to measure growth rates of individual pits in aluminum over 100 h of exposure in a humid, chloride environment. While pits grew at relatively constant rates over the first hours after nucleation, significant growth-rate nonlinearities subsequently occurred. These were linked to both droplet spreading, which altered the cathode size, and changes in the mode of pit growth. Pit morphology appeared to influence the dominant growth mode and the duration of pit growth. Post-mortem serial sectioning revealed pits preferentially attacked grain-boundary triple junctions and dislocation boundaries.

Noell, Philip J. (ORCID:0000000346998999)↗

Correlative chemical and elemental nano-imaging of morphology and disorder at the nacre-prismatic region interface in Pinctada margaritifera

Abstract Understanding biomineralization relies on imaging chemically heterogeneous organic–inorganic interfaces across a hierarchy of spatial scales. Further, organic minority phases are often responsible for emergent inorganic structures from the atomic arrangement of different polymorphs, to nano- and micrometer crystal dimensions, up to meter size mollusk shells. The desired simultaneous chemical and elemental imaging to identify sparse organic moieties across a large field-of-view with nanometer spatial resolution has not yet been achieved. Here, we combine nanoscale secondary ion mass spectroscopy (NanoSIMS) with spectroscopic IR s -SNOM imaging for simultaneous chemical, molecular, and elemental nanoimaging. At the example of Pinctada margaritifera mollusk shells we identify and resolve ~ 50 nm interlamellar protein sheets periodically arranged in regular ~ 600 nm intervals. The striations typically appear ~ 15 µm from the nacre-prism boundary at the interface between disordered neonacre to mature nacre. Using the polymorph distinctive IR-vibrational carbonate resonance, the nacre and prismatic regions are consistently identified as aragonite ( $${\overline{\nu }}_{a}=860$$ ν ¯ a = 860 cm −1 ) and calcite ( $${\overline{\nu }}_{c}=880$$ ν ¯ c = 880 cm −1 ), respectively. We observe previously unreported morphological features including aragonite subdomains encapsulated in extensions of the prism-covering organic membrane and regions of irregular nacre tablet formation coincident with dispersed organics. We also identify a ~ 200 nm region in the incipient nacre region with less well-defined crystal structure and integrated organics. These results show with the identification of the interlamellar protein layer how correlative nano-IR chemical and NanoSIMS elemental imaging can help distinguish different models proposed for shell growth in particular, and how organic function may relate to inorganic structure in other biomineralized systems in general.

54 ENVIRONMENTAL SCIENCES↗

Inferring building height from footprint morphology data

As cities continue to grow globally, characterizing the built environment is essential to understanding human populations, projecting energy usage, monitoring urban heat island impacts, preventing environmental degradation, and planning for urban development. Buildings are a key component of the built environment and there is currently a lack of data on building height at the global level. Current methodologies for developing building height models that utilize remote sensing are limited in scale due to the high cost of data acquisition. Other approaches that leverage 2D features are restricted based on the volume of ancillary data necessary to infer height. Here, we find, through a series of experiments covering 74.55 million buildings from the United States, France, and Germany, it is possible, with 95% accuracy, to infer building height within 3 m of the true height using footprint morphology data. Our results show that leveraging individual building footprints can lead to accurate building height predictions while not requiring ancillary data, thus making this method applicable wherever building footprints are available. The finding that it is possible to infer building height from footprint data alone provides researchers a new method to leverage in relation to various applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Applying MALDI-TOF MS to resolve morphologic and genetic similarities between two Dermacentor tick species of public health importance

Abstract Hard ticks (Acari: Ixodidae) have been historically identified by morphological methods which require highly specialized expertise and more recently by DNA-based molecular assays that involve high costs. Although both approaches provide complementary data for tick identification, each method has limitations which restrict their use on large-scale settings such as regional or national tick surveillance programs. To overcome those obstacles, the matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been introduced as a cost-efficient method for the identification of various organisms, as it balances performance, speed, and high data output. Here we describe the use of this technology to validate the distinction of two closely relatedDermacentortick species based on the development of the first nationwide MALDI-TOF MS reference database described to date. The dataset obtained from this protein-based approach confirms that tick specimens collected from United States regions west of the Rocky Mountains and identified previously asDermacentor variabilisare the recently described species,Dermacentor similis. Therefore, we propose that this integrative taxonomic tool can facilitate vector and vector-borne pathogen surveillance programs in the United States and elsewhere.

Science & Technology - Other Topics↗

Deep learning of structural morphology imaged by scanning X-ray diffraction microscopy

Scanning X-ray nanodiffraction microscopy is a powerful technique for spatially resolving nanoscale structural morphologies by diffraction contrast. One of the critical challenges in experimental nanodiffraction data analysis is posed by the convergence angle of nanoscale focusing optics which creates simultaneous dependency of the far-field scattering data on three independent components of the local strain tensor-corresponding to dilation and two potential rigid body rotations of the unit cell. All three components are in principle resolvable through a spatially mapped sample tilt series; however, traditional data analysis is computationally expensive and prone to artifacts. In this study, we implement NanobeamNN, a convolutional neural network specifically tailored to the analysis of scanning probe X-ray microscopy data. NanobeamNN learns lattice strain and rotation angles from simulated diffraction of a focused X-ray nanobeam by an epitaxial thin film and can directly make reasonable predictions on experimental data without the need for additional fine-tuning. We demonstrate that this approach represents a significant advancement in computational speed over conventional methods, as well as a potential improvement in accuracy over the current standard.

Luo, Aileen [Cornell Univ., Ithaca, NY (United Sta↗