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At least 343 records · Page 19

Expanding standards in viromics: in silico evaluation of dsDNA viral genome identification, classification, and auxiliary metabolic gene curation

Viruses influence global patterns of microbial diversity and nutrient cycles. Though viral metagenomics (viromics), specifically targeting dsDNA viruses, has been critical for revealing viral roles across diverse ecosystems, its analyses differ in many ways from those used for microbes. To date, viromics benchmarking has covered read pre-processing, assembly, relative abundance, read mapping thresholds and diversity estimation, but other steps would benefit from benchmarking and standardization. Here we use in silico-generated datasets and an extensive literature survey to evaluate and highlight how dataset composition (i.e., viromes vs bulk metagenomes) and assembly fragmentation impact (i) viral contig identification tool, (ii) virus taxonomic classification, and (iii) identification and curation of auxiliary metabolic genes (AMGs). The in silico benchmarking of five commonly used virus identification tools show that gene-content-based tools consistently performed well for long (≥3 kbp) contigs, while k -mer- and blast-based tools were uniquely able to detect viruses from short (≤3 kbp) contigs. Notably, however, the performance increase of k -mer- and blast-based tools for short contigs was obtained at the cost of increased false positives (sometimes up to ~5% for virome and ~75% bulk samples), particularly when eukaryotic or mobile genetic element sequences were included in the test datasets. Furthermore, for viral classification, variously sized genome fragments were assessed using gene-sharing network analytics to quantify drop-offs in taxonomic assignments, which revealed correct assignations ranging from ~95% (whole genomes) down to ~80% (3 kbp sized genome fragments). A similar trend was also observed for other viral classification tools such as VPF-class, ViPTree and VIRIDIC, suggesting that caution is warranted when classifying short genome fragments and not full genomes. Finally, we highlight how fragmented assemblies can lead to erroneous identification of AMGs and outline a best-practices workflow to curate candidate AMGs in viral genomes assembled from metagenomes. Together, these benchmarking experiments and annotation guidelines should aid researchers seeking to best detect, classify, and characterize the myriad viruses ‘hidden’ in diverse sequence datasets.

59 BASIC BIOLOGICAL SCIENCES↗

Statistical White-Line Analysis in High-Throughput TXM-XANES for Chemical State Quantification

The transmission X-ray microscopy (TXM) based X-ray absorption near-edge structure (XANES) technique provides three-dimensional mapping of element-specific chemical states at nanometer-scale spatial resolution and micrometer-scale fields of view. However, compared to conventional volume-averaged XANES (VA-XANES) measurements, the inherently small voxel size in TXM-XANES leads to a lower signal-to-noise ratio, making full-spectrum analysis computationally demanding and less robust. Here, we present the structural and compositional conditions for a statistical white-line analysis framework under which chemical state information can be directly extracted from the white-line peak position in voxel spectra without the need for voxel-wise background subtraction or normalization, under well-defined structural and compositional conditions. The method is validated on layered oxide cathode materials, where low-order polynomial fitting accurately reproduces white-line features, and the extracted energy distributions correlate strongly with VA-XANES results. This statistical approach enables high-throughput, dose-efficient, and noise-robust chemical state quantification in TXM-XANES, offering broad applicability to functional materials requiring nanoscale oxidation-state mapping.

TXM↗

Cation-Driven Assembly of Bilayered Vanadium Oxide and Graphene Oxide Nanoflakes to Form Two-Dimensional Heterostructure Electrodes for Li-Ion Batteries

Lithium preintercalated bilayered vanadium oxide (LVO or δ-Li x V 2 O 5 ·nH 2 O) and graphene oxide (GO) nanoflakes were assembled using a concentrated lithium chloride solution and annealed under vacuum at 200 °C to form two-dimensional (2D) δ-Li x V 2 O 5 ·nH 2 O and reduced GO (rGO) heterostructures. Here we found that the Li + ions from LiCl enhanced the oxide/carbon heterointerface formation and served as stabilizing ions to improve structural and electrochemical stability. The graphitic content of the heterostructure could be easily controlled by changing the initial GO concentration prior to assembly. We found that increasing the GO content in our heterostructure composition helped inhibit the electrochemical degradation of LVO during cycling and improved the rate capability of the heterostructure. A combination of scanning electron microscopy and X-ray diffraction was used to help confirm that a 2D heterointerface formed between LVO and GO, and the final phase composition was determined using energy-dispersive X-ray spectroscopy and thermogravimetric analysis. Scanning transmission electron microscopy and electron energy-loss spectroscopy were additionally used to examine the heterostructures at high resolution, mapping the orientations of rGO and LVO layers and locally imaging their interlayer spacings. Further, electrochemical cycling of the cation-assembled LVO/rGO heterostructures in Li-ion cells with a non-aqueous electrolyte revealed that increasing the rGO content led to improved cycling stability and rate performance, despite slightly decreased charge storage capacity. The heterostructures with 0, 10, 20, and 35 wt % rGO exhibited capacities of 237, 216, 174, and 150 mAh g –1 , respectively. Moreover, the LVO/rGO-35 wt % and LVO/rGO-20 wt % heterostructures retained 75% (110 mAh g–1) and 67% (120 mAh g –1 ) of their initial capacities after increasing the specific current from 20 to 200 mA g –1 , while the LVO/rGO-10 wt % sample retained only 48% (107 mAh g –1 ) of its initial capacity under the same cycling conditions. In addition, the cation-assembled LVO/rGO electrodes exhibited enhanced electrochemical stability compared to electrodes prepared through physical mixing of LVO and GO nanoflakes in the same ratios as the heterostructure electrodes, further revealing the stabilizing effect of a 2D heterointerface. The cation-driven assembly approach, explored in this work using Li + cations, was found to induce and stabilize the formation of stacked 2D layers of rGO and exfoliated LVO. The reported assembly methodology can be applied for a variety of systems utilizing 2D materials with complementary properties for applications as electrodes in energy storage devices.

25 ENERGY STORAGE↗

Effect of void positioning on the detonation sensitivity of a heterogeneous energetic material

We show although it is well-established that voids profoundly influence the initiation and reaction behaviors of heterogeneous energetic materials such as polymer-bonded explosives (PBX) and propellants, there has been little study of how void location in different constituents in the microstructures of such materials affect the macroscale behavior. Here, we use three-dimensional (3D) mesoscale simulations to study how void placement within the reactive grains versus the polymer binder influences the shock-to-detonation transition (SDT) in a polymer-bonded explosive. The material studied here has a microstructure comprised of 75% PETN (pentaerythritol tetranitrate) grains and 25% HTPB (hydroxyl-terminated polybutadiene) polymer binder by volume. Porosities up to 10% in the form of spherical voids distributed in both the grains and polymer are considered. An Arrhenius reactive burn relation is used to model the chemical kinetics of the PETN grains under shock loading, thereby resolving the heterogeneous detonation behavior of the PBX. The influence of void location on the shock initiation sensitivity of the material is quantitatively ranked by comparing the predicted run distance to detonation (RDD) for each sample. The analysis includes inherent quantification of uncertainties arising from the stochastic variations in the microstructure morphologies and void distributions by using statistically equivalent microstructure sample sets (SEMSS), leading to probabilistic formulations for the RDD as a function of shock pressure. The calculations reveal that the location of voids in the composite microstructure significantly affects the RDD. Specifically, voids exclusively within the grains cause the PBX to be more sensitive (having shorter RDD) than voids in the polymer binder. Unique probabilistic relationships are derived to map the probability of observing RDD for each void location material case, allowing for prediction of initiation behavior anywhere in the shock pressure – RDD space. These findings agree with trends reported in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Endogenic and Exogenic Contributions to Visible-wavelength Spectra of Europa’s Trailing Hemisphere

The composition of Europa’s trailing hemisphere reflects the combined influences of endogenous geologic resurfacing and exogenous sulfur radiolysis. Using spatially resolved visible-wavelength spectra of Europa obtained with the Hubble Space Telescope, we map multiple spectral features across the trailing hemisphere and compare their geographies with the distributions of large-scale geology, magnetospheric bombardment, and surface color. Based on such comparisons, we interpret some aspects of our spectra as indicative of purely exogenous sulfur radiolysis products and other aspects as indicative of radiolysis products formed from a mixture of endogenous material and magnetospheric sulfur. The spatial distributions of two of the absorptions seen in our spectra—a widespread downturn toward the near-UV and a distinct feature at 530 nm—appear consistent with sulfur allotropes previously suggested from ground-based spectrophotometry. However, the geographies of two additional features—an absorption feature at 360 nm and the spectral slope at red wavelengths—are more consistent with endogenous material that has been altered by sulfur radiolysis. We suggest irradiated sulfate salts as potential candidates for this material, but we are unable to identify particular species with the available data.

79 ASTRONOMY AND ASTROPHYSICS↗

Tools for uranium characterization in carbonate samples: case studies of natural U–Pb geochronology reference materials

Laser ablation U–Pb analyses of carbonate (LAcarb) samples has greatly expanded the potential for U–Pb dating to a variety of carbonate-producing settings. Carbonates that were previously considered impossible to date using isotope dilution methods may preserve radiogenic domains that can be dated using spatially resolved laser ablation geochronology techniques. Work is ongoing to identify reference materials and to consider best practices for LAcarb. In this study we apply standard and emerging characterization tool sets on three natural samples with the dual goal of enhancing the study of carbonates and establishing a new set of well-characterized natural reference materials for LAcarb studies. We start with the existing carbonate reference material WC-1 from the Permian Reef Complex of Texas, building on the published description to offer a deeper look at U and associated trace elements. We consider a tufa sample from the Miocene Barstow Formation of the Mojave Block, California, as a possible secondary calcite reference material due to its well-behaved U–Pb systematics. There are currently no natural dolomite standards. We present an unusual dolomite sample with very well-behaved U–Pb systematics from the Miocene of the Turkana Basin of Kenya as a possible dolomite reference material for LAcarb dating. In addition to using X-ray fluorescence (XRF) mapping and spectroscopy to better understand U in these natural samples, we have analyzed multiple aliquots of each of them for 87 Sr/ 86 Sr by thermal ionization mass spectrometry (TIMS). The Sr isotope compositions are analytically homogeneous within petrographically homogeneous regions of all three samples, and thus these materials could be used as Sr isotope standards as well. While not part of the current contribution, this combination could streamline simultaneous LA analyses of 87 Sr/ 86 Sr and U–Pb geochronology.

36 MATERIALS SCIENCE↗

MSW Variability Mapping and Conversion to Biofuel

MSW (Municipal Solid Waste) is a form of biomass which consists of categorized components of waste/trash. The general categories are paper, yard trash, construction & debris, appliances, tires, glass, metals, aluminum & steel cans, plastics, organics, inorganics, and HHW (Household Hazardous Waste). This project focuses on the factors within a region or population that contribute to variability in the composition of MSW and in turn MSW’s convertibility to biofuel. A list of contributors was determined (Social Vulnerability Index, Access to Public Transportation, Racial Distribution, GDP, Personal Income) and then JMP was used to perform a Multivariate analysis to determine correlations and a Partial Least-Squares regression to determine Variable Importance Plots for each MSW category. In addition to data analysis, the convertibility of MSW to biofuel was studied via microwave pyrolysis system in order to separate and characterize the various gaseous and bio-oil products.

09 BIOMASS FUELS↗

A NICER View of the Massive Pulsar PSR J0740+6620 Informed by Radio Timing and XMM-Newton Spectroscopy

We report on Bayesian estimation of the radius, mass, and hot surface regions of the massive millisecond pulsar PSR J0740+6620, conditional on pulse-profile modeling of Neutron Star Interior Composition Explorer X-ray Timing Instrument event data. We condition on informative pulsar mass, distance, and orbital inclination priors derived from the joint North American Nanohertz Observatory for Gravitational Waves and Canadian Hydrogen Intensity Mapping Experiment/Pulsar wideband radio timing measurements of Fonseca et al. We use XMM-Newton European Photon Imaging Camera spectroscopic event data to inform our X-ray likelihood function. The prior support of the pulsar radius is truncated at 16 km to ensure coverage of current dense matter models. We assume conservative priors on instrument calibration uncertainty. We constrain the equatorial radius and mass of PSR J0740+6620 to be ${12.39}_{-0.98}^{+1.30}$ km and ${2.072}_{-0.066}^{+0.067}$ M ⊙ respectively, each reported as the posterior credible interval bounded by the 16% and 84% quantiles, conditional on surface hot regions that are non-overlapping spherical caps of fully ionized hydrogen atmosphere with uniform effective temperature; a posteriori, the temperature is ${\mathrm{log}}_{10}(T\,[{\rm{K}}])={5.99}_{-0.06}^{+0.05}$ for each hot region. All software for the X-ray modeling framework is open-source and all data, model, and sample information is publicly available, including analysis notebooks and model modules in the Python language. Furthermore, our marginal likelihood function of mass and equatorial radius is proportional to the marginal joint posterior density of those parameters (within the prior support) and can thus be computed from the posterior samples.

79 ASTRONOMY AND ASTROPHYSICS↗

Offshore Wind Composite Siting Exclusions Scenarios

This dataset consolidates criteria that restrict the siting of offshore wind energy installations, an update from Zuckerman et al. (2023). All scenarios exclude area from wind energy development due to legal or administrative restrictions (e.g., Marine Protected Areas), existing infrastructure, and technical constraints (e.g., 1,300 m bathymetry limit). A TIF data file and a PNG cartographic map of the data are provided for three scenarios ("Open", "Reference", and "Limited"), showing areas where offshore wind energy is restricted across the contiguous United States. The "Open" scenario only excludes areas with known preclusions for offshore wind deployment. The "Reference" scenario excludes all areas from the "Open" scenario, as well as additional best management practices such as known proposed protected areas, and state waters. The "Limited" scenario excludes all area from the "Reference" scenario. Additionally, it has more stringent siting criteria such as larger setbacks from shore and infrastructure, as well as shallower depth limits on floating technology. For further details and citation, please refer to the publication linked below: Zuckerman, Gabriel R., Anthony Lopez, Travis Williams, Rebecca Green, and Grant Buster. 2023. Impacts of Siting Considerations on Offshore Wind Technical Potential in the United States. Golden, CO: National Renewable Energy Laboratory. NREL/TP-6A20- 85088.

Array↗

Deep learning models map rapid plant species changes from citizen science and remote sensing data

Anthropogenic habitat destruction and climate change are reshaping the geographic distribution of plants worldwide. However, we are still unable to map species shifts at high spatial, temporal, and taxonomic resolution. Here, we develop a deep learning model trained using remote sensing images from California paired with half a million citizen science observations that can map the distribution of over 2,000 plant species. Our model— Deepbiosphere— not only outperforms many common species distribution modeling approaches (AUC 0.95 vs. 0.88) but can map species at up to a few meters resolution and finely delineate plant communities with high accuracy, including the pristine and clear-cut forests of Redwood National Park. These fine-scale predictions can further be used to map the intensity of habitat fragmentation and sharp ecosystem transitions across human-altered landscapes. In addition, from frequent collections of remote sensing data, Deepbiosphere can detect the rapid effects of severe wildfire on plant community composition across a 2-y time period. These findings demonstrate that integrating public earth observations and citizen science with deep learning can pave the way toward automated systems for monitoring biodiversity change in real-time worldwide.

Gillespie, Lauren E.↗

Cosolvent-tuned interactions in ionic liquids: A vibrational and quantum-chemical study of ethylene glycol ratio effects

Ionic liquids (ILs) are attractive media for CO 2 capture but remain limited by viscosity and cost. Blending ILs with ethylene glycol (EG) is a practical route to mitigate these constraints, yet the molecular origins of cosolvent effects and their dependence on composition are not well resolved. We combine Fourier-transform infrared (FT-IR) spectroscopy with quantum-chemical (DFT) analysis to elucidate how the IL:EG molar ratio modulates intermolecular interactions and electronic structure. Computed vibrational frequencies enable mode assignment and deconvolution of overlapping bands, revealing systematic, ratio-dependent shifts and broadenings in (i) EG O–H stretching, (ii) cation and EG C–H stretchings (imidazolium C2–H, C4–H, C5–H, methyl and ethyl groups, -CH2 of EG), (iii) anion signature modes (e.g., CN motifs), and (iv) EG C–O and C–C stretchings, consistent with the redistribution of hydrogen-bonding networks. Molecular electrostatic potential (MESP) maps quantify attenuation of extreme potential regions with increasing EG, indicating progressive screening of cation–anion electrostatic interactions. Quantum Theory of Atoms in Molecules (QTAIM) identifies emergent bond critical points between EG and the IL ions, while Reduced Density Gradient–Noncovalent Interaction (RDG–NCI) analysis differentiates strong directional hydrogen bonds from dispersive contacts across compositions. Together, these results show that EG fraction controls a switch from predominantly ion–ion to mixed ion–EG coordination, altering local polarity and polarizability that underlie the observed FT-IR trends. The framework provides composition–structure–spectrum relationships that can guide rational selection of IL:EG ratios to balance favorable molecular interactions with practical performance targets in scalable CO 2 capture systems.

DAC↗

Hyperspectral x-ray imaging mapping capabilities for nuclear forensics

Nuclear forensics relies on the integration of complementary signatures to constrain the origins and history of materials. Outcomes benefit from the timeliness and precision of the disparate methods that form typical analysis chains. Sample forms are often either minute in quantity or contain signatures like morphology or composition heterogeneity encoded on a microscale, so many analysis techniques focus on resolving signatures on ever-smaller length scales. The new hyperspectral x-ray imaging (HXI) instrument developed at Los Alamos National Laboratory seeks to improve the information available from scanning electron microscopy (SEM) x-ray spectrum analysis through superior spectral energy resolution vs. typical energy dispersive spectroscopy (EDS) systems in common use in nuclear forensics and other microanalysis fields. Based on arrays of transition-edge sensor (TES) microcalorimeter detectors, this instrument achieves a typical energy resolution of 7 eV full-width at half-maximum (FWHM) at 2 keV, opening new possibilities in trace element detection/analysis and chemical state determination through spectral shape shifts. We present here some of the first applications of the HXI instrument to actinide samples and discuss potential maturation of this nascent technology for future analysis pipelines.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Determination of fluorine distribution in shark teeth by laser-induced breakdown spectroscopy

Quantifying the chemical composition of fast-growing hard tissues in the environment can shed valuable information in terms of understanding ecosystems both prehistoric and current. Changes in chemical composition can be correlated with environmental conditions and can provide information about the organism's life. Sharks can lose 0.1 to 1.1 teeth/day, depending on species, which offers a unique opportunity to record environmental changes over a short duration of time. Shark teeth contain a biomineral phase that is made up of fluorapatite [Ca 5 (PO 4 ) 3 F], and the F distribution within the tooth can be correlated to tooth hardness. Typically, this is determined by bulk acid digestion, energy-dispersive X-ray spectroscopy (EDS), or wavelength-dispersive spectroscopy. Here we present laser-induced breakdown spectroscopy (LIBS) as an alternative and faster approach for determining F distribution within shark teeth. Using a two-volume laser ablation chamber (TwoVol3) with innovative embedded collection optics for LIBS, shark teeth were investigated from sand tiger (Carcharias Taurus), tiger (Galeocerdo Cuvier), and hammerhead sharks (Sphyrnidae). Fluorine distribution was mapped using the CaF 603 nm band (CaF, Β 2 Σ + → X 2 Σ + ) and quantified using apatite reference materials. In addition, F measurements were cross referenced with EDS analyses to validate the findings. Distributions of F (603 nm), Na (589 nm), and H (656 nm) within the tooth correlate well with the expected biomineral composition and expected tooth hardness. This rapid methodology could transform the current means of determining F distribution, particularly when large sample specimens (350 mm 2 , presented here) and large quantities of specimens are of interest.

36 MATERIALS SCIENCE↗

Calcareous organic matter coatings sequester siderophores in alkaline soils

Although most studies on organic matter stabilization in soils have focused on adsorption to aluminosilicate and iron oxide minerals due to their strong interactions with organic nucleophiles, stabilization within alkaline soils has been empirically correlated with exchangeable Ca concentrations. Yet the extent of competing processes within natural soil remain unclear. We employed sub-micron scale techniques to investigate the minerology and organic carbon on individual fine particles within an alkaline soil from Eastern Washington. XRD, Mössbauer spectroscopy, TEM-EDX-SAED, and XPS analysis demonstrated a mineral assemblage dominated by quartz, feldspars, iron oxides, and calcite. Although exposed Si, Al, and Fe accounted for ~30% of the surface elemental composition, most of the organic carbon and nitrogen was associated with Ca-rich coatings. Adsorption isotherms of two siderophores with the same soil showed greater adsorption of pyoverdine compared with less polar enterobactin. Using NanoSIMS to map the distribution of isotopically labeled siderophores across the surfaces of fine grains, we observed a preference for binding to surfaces heavily coated with organic matter. We propose a mechanism of adsorption by which organic molecules aggregate within calcareous soils via calcium bridging, favoring the stabilization of larger molecules with a greater number of nucleophilic functional groups.

54 ENVIRONMENTAL SCIENCES↗

Landscape-scale characterization of Arctic tundra vegetation composition, structure, and function with a multi-sensor unoccupied aerial system

The Arctic is experiencing some of the most rapid climate change on Earth, with strong impacts on tundra ecosystems that are characterized by high land-surface and vegetation heterogeneity. Previous studies have explored this complexity using satellite remote sensing, however these typically coarse spatial resolution data have generally missed sub-pixel heterogeneity, leaving critical gaps in our understanding of tundra vegetation dynamics from the community to landscape scales. To address these gaps, we collected very high-resolution (1-5 cm) optical, structural, and thermal data at three low-Arctic tundra sites on the Seward Peninsula, Alaska, using a multi-sensor unoccupied aerial system (UAS). We examined the application of these data to studying tundra vegetation dynamics, by quantifying (1) canopy height and thermoregulation (leaf-air temperature) of representative plant functional types (PFTs), (2) fine-scale patterns of vegetation composition across landscapes, and (3) impacts of fine-scale vegetation composition on landscape-scale variation of canopy height and thermoregulation. Our results show that deciduous tall shrubs (those that can potentially grow >2 m) had a strong cooling effect, with canopy temperatures significantly lower than local air temperatures and other PFTs. Increased cover of tall shrubs also had the potential to reduce the cover of low-stature PFTs across the landscape, potentially associated with their closed canopy (i.e., increased light competition) and strong thermoregulation. To understand the connections between fine-scale vegetation composition and large-scale ecosystem processes, we produced a random forest model which showed that fine-scale PFT composition accounted for 86.8% and 74.2% of the landscape-scale variation in canopy height and thermoregulation, respectively. These findings highlight the importance of spatially detailed characterization of tundra PFTs to improve our ecological understanding and model representation of tundra vegetation, also transcend our study to show the need for continued collection of similar datasets to better understand the impacts of surface heterogeneity on the mapping and modeling of tundra ecosystem dynamics, as well as assist with conservation management and biodiversity monitoring strategies.

54 ENVIRONMENTAL SCIENCES↗

Topography and electrostatic interactions of electret fibres in N95 facemasks

Facemasks have been a critical line of defense in the Covid-19 pandemic and have been used for decades to reduce the inhalation of sub-micron aerosols, including bacteria, viruses and nano-materials. These facemasks leverage electrostatic charge properties of non-woven electret fibre mats to remove sub-micron aerosols. However, the topographical and electrostatic properties of these mats have not been well characterized at the nano-scale. In this study, we use atomic force microscopy (AFM) to examine the surface topography of the electret fibres within a commercial respirator fibre mat, use electrostatic force microscopy to map the electrostatic interactions emanating from these fibres, and use synchrotron X-ray scattering to probe polymer morphology. We find that within these mats the fibres exhibit significant heterogeneity in surface topography, electrostatic interactions and polypropylene phase composition. The surface topographies ranged from nano-smooth surfaces to ordered spherulitic structures. Furthermore, the electrostatic interactions varied across fibre length and circumference and are only weakly correlated with surface topographical features. Finally, we use AFM to characterize fibres after filtering a NaCl aerosol and find that the deposited particles are heterogeneous in size and distributed over the fibre surfaces.

36 MATERIALS SCIENCE↗

Kinetics and Reaction Mechanisms of Acetic Acid Hydrodeoxygenation over Pt and Pt–Mo Catalysts

In this work, kinetic measurements for silica-supported Pt and Pt-Mo catalysts were collected in vapor-phase acetic acid hydrodeoxygenation by varying the hydrogen partial pressure between 18 and 72 kPa and acetic acid partial pressure between 7 and 18 kPa at 423-473 K. At all testing conditions, the Pt-Mo catalyst was more active and selective. In addition, the apparent activation energy for Pt-Mo of 76±3 kJ/mol was lower than that of 84±4 kJ/mol for Pt. The apparent reaction orders were also different. The order in hydrogen of 0.8±0.1 for Pt-Mo changed to zero at higher hydrogen partial pressures while that for Pt remained constant at 0.6±0.1. A near-zero order in acetic acid for Pt-Mo changed to -2.1 at higher acetic acid pressures while that for Pt remained constant at -2.9±0.3. These differences in reaction kinetics as well as in selectivity trends with changes in temperature and feed composition indicated a change in the reaction mechanism for Pt-Mo. The catalysts were characterized with hydrogen temperature programmed desorption, oxygen temperature programmed oxidation and transmission electron microscopy with energy-dispersed X-ray spectroscopy elemental mapping. Mo was present in the form of subnanometer-size clusters on the surface of Pt nanoparticles. Both Pt and Pt-Mo catalysts were stable under the reaction conditions for 10 h, and the size and structure of Pt and Pt-Mo particles remained mostly unchanged, without coke accumulation. Density functional theory calculations show that surface acetate is not a major reaction intermediate on both Pt and Pt-Mo and, instead, C-OH bond splitting with the formation of acetyl is the first reaction step in hydrodeoxygenation. The activation energy for this step is dramatically lower on Pt-Mo. Furthermore, the activity of acetyl on Pt-Mo is different. Unlike on pure Pt, the reaction of C-O bond splitting becomes exothermic with a lower activation energy on Pt-Mo, and the reaction of C-C bond splitting, in contrast, becomes endothermic with a higher activation energy, explaining the experimentally observed higher activities and selectivities of Pt-Mo. In addition, the calculations demonstrate that a pair of Pt-Mo surface atoms acts as a single active site where Mo serves as a preferential binding anchor for O atoms. The presence of Mo atoms changes the structure and energy of adsorbed and reacting surface species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

AFM-IR and s-SNOM-IR measurements of chemically addressable monolayers on Au nanoparticles

The performance of catalysts depends on their nanoscale properties, and local variations in structure and composition can have a dramatic impact on the catalytic reactivity. Therefore, probing the localized reactivity of catalytic surfaces using high spatial resolution vibrational spectroscopy, such as infrared (IR) nanospectroscopy and tip-enhanced Raman spectroscopy, is essential for mapping their reactivity pattern. Two fundamentally different scanning probe IR nanospectroscopy techniques, namely, scattering-type scanning near-field optical microscopy (sSNOM) and atomic force microscopy-infrared spectroscopy (AFM-IR), provide the capabilities for mapping the reactivity pattern of catalytic surfaces with a spatial resolution of ~20 nm. Herein, we compare these two techniques with regard to their applicability for probing the vibrational signature of reactive molecules on catalytic nanoparticles. For this purpose, we use chemically addressable self-assembled molecules on Au nanoparticles as model systems. We identified significant spectral differences depending on the measurement technique, which originate from the fundamentally different working principles of the applied methods. While AFM-IR spectra provided information from all the molecules that were positioned underneath the tip, the s-SNOM spectra were more orientation-sensitive. Due to its field-enhancement factor, the s-SNOM spectra showed higher vibrational signals for dipoles that were perpendicularly oriented to the surface. The s-SNOM sensitivity to the molecular orientation influenced the amplitude, position, and signal-to-noise ratio of the collected spectra. Ensemble-based IR measurements verified that differences in the localized IR spectra stem from the enhanced sensitivity of s-SNOM measurements to the adsorption geometry of the probed molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗