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At least 19 records

Capturing Surface Coverage Effects in Heterogeneous Catalysis

Adsorbate–adsorbate lateral interactions at relevant surface coverages have a significant effect on chemical kinetics, thereby influencing the activity of a heterogeneous catalyst. Coverage-dependent kinetic and thermodynamic parameters therefore must be included in studies of such complex systems to properly predict the turnover frequencies and kinetic trends. Thus, it becomes extremely important to accurately capture the strength of lateral interactions between neighboring species under realistic reaction conditions. In this Perspective, we discuss the various existing computational and experimental methods for determining adspecies coverage and configurational effects. The choice of the tools and methods employed in such studies depends on factors such as time, length scales, computational cost, the presence of solvents, and reaction conditions. The applications of each method and the respective challenges are also discussed here. As a result, we discuss the recent developments and future of the state-of-the-art for inclusion of surface coverage and configuration into a holistic picture for accurate predictions of catalytic behavior.

09 BIOMASS FUELS

Anolyte Buffering and CO Coverage Effects in the Electrochemical Reduction of CO at Cu Electrocatalysts

Electrolytic CO reduction was investigated at copper electrocatalysts in zero-gap membrane electrode assemblies as a function of buffering agents and cofeeding with CO 2 or Ar. Results show an acetate Faradaic efficiency (FE) of 90% at 300 mA cm −2 using pure CO feeds and phosphate-buffered anolyte near pH 8. When using CO feeds with more alkaline anolytes, the hydrogen evolution reaction becomes the dominant reduction reaction, independent of the buffer. Product distributions of cofeeding experiments with CO and CO 2 show that increasing CO 2 cofeeding results in increased selectivity toward ethylene (42% FE) in near-neutral KHCO 3 anolytes or ethanol (40% FE) in alkaline KOH anolytes. Evaluation of several commercial anion exchange membranes shows similar selectivity trends, suggesting product selectivity is dominated by the local pH and surface coverage of CO. Based on these results, we propose pH buffering and CO coverage behaviors that facilitate high selectivities to acetate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Adsorption of CO on gold: effect of coverage and surface deformations

Recent insights into the nature of catalysts under reactive conditions have motivated investigating heterogeneously catalyzed reactions with non-rigid surfaces. As an example system to revisit, CO interactions with gold have been a longstanding system of interest due to its structure sensitivity. In this work, we investigate coverage-dependent CO adsorption trends on terraces, steps, and kinks. Calculating differential binding energy and mean absolute displacement of the atomic structures as a function of CO coverage, we propose a deformation quenching mechanism that partially determines CO saturation coverage. Extending this analysis to consider CO partial pressure, we show a phase change in CO step occupation, which we highlight as a possible explanation for previously reported temperature-programmed desorption and Fourier-transform infrared reflection-absorption spectroscopy measurements. Furthermore, this work shows how adopting a non-rigid surface model can lead to additional insights which may be applied to other heterogeneously catalyzed systems.

Kavalsky, Lance [University of Wisconsin-Madison,

Adsorption, charge transfer and a coverage-driven transition of alkali metals on rutile TiO 2 (110)

The interaction of alkali metals with metal oxide surfaces is central to tuning surface reactivity in heterogeneous catalysis and photocatalysis. Here we present a comprehensive DFT+U study of the adsorption of alkali metals (Li, Na, K, Rb, Cs) on the (110) surface of rutile TiO 2 . At low coverage (θ = 1/8), all alkali metals bind preferentially to bridging oxygen sites with adsorption energies in the range −4.06 to −3.33 eV, transferring nearly one full electron (0.92–0.99 |e|) to the substrate and inducing Ti 4+ → Ti 3+ reduction. The excess charge localizes preferentially at subsurface Ti sites in the form of small polarons. Diffusion barriers indicate facile motion along bridging-oxygen rows, whereas inter-row hopping is strongly hindered. Coverage effects were examined systematically for potassium: adsorption energy and charge transfer per K atom decrease monotonically with increasing θ. Strikingly, a sharp energy discontinuity occurs between θ = 4/8 and θ = 5/8 (ΔE ≈ 1 eV per atom), which we identify as a coverage-driven structural transition arising from steric packing constraints and enhanced K–K electrostatic repulsion once every (1×1) surface cell is occupied. This structural transition perfectly correlates with a dramatic drop in the work function down to an ultra-low minimum of 0.84 eV at θ=5/8, followed by a metallization- driven recovery at higher coverages. Ab initio molecular dynamics simulations confirm zigzag K arrangements at moderate coverage (θ = 1/3), while at high coverage (θ = 2/3) short-range K–K correlations emerge without long-range order. These results provide atomistic insight into the structure–activity relationships underlying alkali promotion effects on oxide-supported catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Identification of Carbonyl Species on Palladium Supported on Ceria in Complex Microenvironments

Herein, we present a systematic comparison between Pd carbonyl (Pd-CO) species, specifically over Pd/CeO 2 based catalysts, observed during isothermal adsorption and in several prototypical catalytic reactions to identify and understand CO adsorption on palladium-ceria based catalysts. Pd-CO is observed via DRIFTS to probe the gas-solid conditions, while ATR-IR is used to probe the affinity of Pd-CO under more complex solvated gas-solid-liquid conditions to discern the influence of the microenvironments for carbonyl adsorption. Here, we explore the presence of Pd-CO under several reactive environments, including CO adsorption, CO 2 + H 2 , CO + H 2 , CH 4 + CO 2 and CO under gas-solid-liquid media, highlighting reactions with notable Pd-CO formation. The differences between palladium carbonyls and carbonate species show that carbonyl species are much more affected via a shifting of the peak position than carbonates, which remain static irrespective of the immediate chemical environment. By following the rate of CO accumulation via K-M mode DRIFTS, we observe migration from linear, 2095 cm -1 , to bridge site, 1978 cm -1 , as a function of time under a static CO atmosphere. With the use of DFT, we discerned changes in Pd-carbonyl stretches due to both coverage effects of CO under simulated reaction conditions and temperature effects. Regardless of whether CO is formed as an intermediate or a reactant, the competitive adsorption of *H and *CO affects the binding strength of *CO at all temperatures, with low temperature favoring atop binding and high temperature favoring the more stable FCC Pd-CO site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

A Lens into the Cu Nanograin by In Situ Vibrational Spectroscopy

Cu-based catalysts are uniquely capable of C-C coupling during electrochemical CO 2 reduction (CO 2 R), yet further mechanistic understanding remains hampered by the lack of spectroscopically resolved descriptors that demonstrate how surface adsorbates emerge and evolve within their catalytic environment. Here, in this study, we correlate in situ surface-enhanced Raman spectroscopy (SERS) and surface-enhanced infrared absorption spectroscopy (SEIRAS) to resolve the potential-dependent dynamics during CO 2 R on Cu nanograin catalysts. By building on previous benchmarking of low overpotential performance and nanograin structural evolution, we offer a diagnostic framework linking vibrational signatures to catalytic function, unveiling which species appear, persist, and turnover as the electrified surface and interfacial environment evolve under bias. The onset of linear CO is marked below -0.45 V, coincident with persistent adsorbed *OH/*O domains beyond the CO 2 R onset. In this context, Cu nanograins serve as a platform to dissect contributions of adsorbate coverage. By carefully dissecting the potential dependence of emergent twin-defect/step CO stretch bands (P1-P2), alongside the prototypical terrace-site CO stretch band (P3), we provide important context for interpreting coupled spectroscopic trends driven by coverage effects and resolve this for the evidently complex nanograin morphology. Together, these observations highlight the intertwined roles of surface stabilization and interfacial flux in steering multicarbon product formation. By directly linking vibrational signatures to catalytic behavior, this work aims to bridge the gap between observation and control and help guide toward a predictive framework of fine-tuned selectivity for CO 2 R.

Fonseca Guzman, Maria V. [University of California

X-ARAPUCA Photon Detectors in SBND

The Short-Baseline Near Detector (SBND) is a liquid argon time projection chamber (LArTPC) for detecting neutrinos from Fermilab's Booster Neutrino Beam. Located 110 m downstream of the beam target, SBND collects both ionization electrons and scintillation photons from particle interactions within the detector volume. The photon detection system (PDS) consists of both PMTs and X-ARAPUCAs, a novel technology featuring large area cost-effective coverage with single photo-electron resolution at cryogenic temperatures. SBND utilizes two types of X-ARAPUCAs: one sensitive to vacuum ultra-violet (VUV) scintillation light produced and one sensitive to visible light for the light reflected off TPB-coated reflective foils. SBND is the only experiment currently testing the X-ARAPUCA technology in a neutrino beam over a period of several years, and will provide critical information for deployment in future detectors like DUNE. This poster will cover the calibration and early performance of X-ARAPUCAs in SBND.

Dalager, Olivia [Fermilab]

Methanol Partial Oxidation on Cu(111) and PtCu(111) Single-Atom Alloy Surfaces: Effect of Surface Oxygen Coverage on Selectivity

The selective oxidation of methanol to formaldehyde on Cu surfaces is an important and well-studied reaction. However, a systematic analysis of product selectivity as a function of oxygen coverage on Cu(111) and Cu-based single-atom alloys (SAAs) has not been previously reported. In this work, we present a comprehensive investigation of deuterated methanol (CD 3 OH) partial oxidation on Cu(111) and 1% PtCu(111) SAA surfaces as a function of preadsorbed oxygen coverage. Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) reveal that isolated Pt atoms inhibit the initial surface oxidation of Cu(111) under low oxygen exposures. Despite this difference in oxidation kinetics, the product selectivity remains largely unaffected: on both Cu(111) and PtCu(111), formaldehyde (CD 2 O) is the predominant partial oxidation product over a broad range of oxygen coverages. The selectivity toward formaldehyde peaks at intermediate oxygen coverages (∼0.3 monolayers, ML), indicating the existence of an optimal oxygen loading for partial oxidation. Notably, the similar product selectivities on Cu(111) and PtCu(111) over a range of surface oxygen coverage indicate that Pt single atoms do not significantly alter the reaction pathway or shift the optimal oxygen coverage for formaldehyde formation. Control experiments confirm that Cu(111) is unreactive toward methanol in the absence of oxygen, while PtCu(111) surfaces produce a small amount of formaldehyde even when oxygen is not preadsorbed, indicating that isolated Pt atoms facilitate O−H activation at below 150 K, leading to H 2 desorption, followed by C−D activation at higher temperatures (∼350 K). Density functional theory (DFT)-based calculations show that Pt atoms increase the O 2 dissociation barrier relative to Cu(111), consistent with the observed inhibition of oxidation at low exposures. Overall, this work provides the first detailed selectivity map for methanol oxidation on oxidized Cu(111) and PtCu(111) SAA surfaces. By linking classical mechanistic insights such as methoxy- and formate-mediated pathways with single-atom alloy catalyst design, this work demonstrates that while Pt substitution modulates the oxidation kinetics and oxygen binding, the overall selectivity toward formaldehyde is governed primarily by oxygen coverage. These findings underscore the potential of isolated dopants to tune surface oxidation behavior without compromising the intrinsic partial oxidation selectivity of copper-based catalysts.

36 MATERIALS SCIENCE

Examining Aerosol Vertical Transport and Removal during Deep Convective Events

Atmospheric aerosols affect the global energy budget by scattering and absorbing sunlight (direct effects) and by changing the microphysical structure, lifetime, and coverage of clouds (indirect effects). Globally, the free troposphere is a major source of nucleation- and Aitken-mode aerosols due to the enhanced new particle formation rates at high altitudes. Recent studies have shown deep convective systems are capable of transporting these small aerosols from the free troposphere to the boundary layer by strong convective downdrafts and weaker downward motions in the stratiform regions. These vertically transported aerosols can grow into cloud condensation nuclei (CCN) and play a significant role in the global climate. During the deep convective processes, existing accumulation-mode aerosols that act as coagulation sinks of smaller particles are also removed by wet scavenging. Compared to the vertical transport of these particles by entrainment mixing, which is slower but more prevalent, the deep convective downdraft processes may be more rapid and efficient in the vertical transport of aerosols. However, most of the current climate models do not include this mechanism as a source of CCN, mainly because the frequency of deep convective events varies significantly with geographic location and thus their contributions to CCN are unpredictable. We target this critical gap in understanding the vertical transport and removal of aerosols by deep convections. We proposed to analyze a multi-year, multi-site measurement record available from the U.S. Department of Energy (DOE) ARM program, including the observations from the 2014/15 Observations and Modeling of the Green Ocean Amazon (GoAmazon) field campaign, the 2017/18 Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA) field campaign, the 2018/19 Cloud, Aerosol, and Complex Terrain Interactions (CACTI) field campaign, the 2021/22 Tracking Aerosol Convection Interactions Experiment (TRACER) field campaign, and the long-term measurements collected at the Southern Great Plains (SGP) atmospheric observatory, where deep convective clouds were frequently observed. This project is aimed at the following three objectives: (1) Gaining a detailed and quantitative understanding of the aerosols transported by a convective downdraft and their evolution in the atmosphere; (2) Examining the wet scavenging mechanisms and efficiencies of aerosols at altitudes of deep convective systems based on ground and aircraft measurements; (3) Evaluating the contribution of deep convective systems to CCN as both a source and a sink of atmospheric aerosols and its seasonal variabilities.

54 ENVIRONMENTAL SCIENCES

Beyond traditional diagnostics: Identifying active galactic nuclei using spectral energy distribution fitting in DESI data

Active galactic nuclei (AGN) are typically identified through their distinctive X-ray or radio emissions, mid-infrared (MIR) colors, or emission lines. However, each method captures different subsets of AGN due to signal-to-noise (S/N) limitations, redshift coverage, and extinction effects, underscoring the necessity for a multiwavelength approach for comprehensive AGN samples. This study explores the effectiveness of spectral energy distribution (SED) fitting as a robust method for AGN identification. Using CIGALE optical-MIR SED fits on DESI Early Data Release galaxies, we compare SED-based AGN selection (AGNFRAC ≥ 0.1) with traditional methods including BPT diagrams, WISE colors, X-ray, and radio diagnostics. The SED fitting identifies ∼70% of narrow- and broad-line AGN and 87% of WISE-selected AGN. Incorporating high S/N WISE photometry reduces star-forming galaxy contamination from 62% to 15%. Initially, ∼50% of SED-AGN candidates are undetected by standard methods, but additional diagnostics classify ∼85% of these sources, revealing low-ionization nuclear emission-line regions and retired galaxies potentially representing evolved systems with weak AGN activity. Further spectroscopic and multiwavelength analysis will be essential to determine the true AGN nature of these sources. SED fitting provides complementary AGN identification, unifying multiwavelength AGN selections. This approach enables more complete – albeit somewhat contaminated – AGN samples, which are essential for upcoming large-scale surveys where spectroscopic diagnostics may be limited.

Seyfert

Simulation of metal nanoparticles growth in methane atmosphere of arc discharge: comparison to experiment

A direct current arc discharge in a methane atmosphere is a scalable and sustainable method to produce metal-carbon core–shell nanoparticles and single-walled carbon nanotubes, where a metal catalyst can be continuously supplied through evaporation of an anode made from the catalyst material. The size of catalyst particles is of critical importance as it can affect the synthesis yield and properties of nanotubes and core–shell nanoparticles. This study presents a numerical model describing the formation and growth of metal particles for the conditions representative of the arc discharge with an evaporating iron anode at near-atmospheric pressure of a methane-rich atmosphere. The model incorporates carbon adsorption to the metal surface and explains the limiting effect of carbon coverage on the size of metal nanoparticles. The predicted particle sizes are compared with experimental observations. The model also predicts higher concentrations of metal particles with the increasing partial pressure of methane.

77 NANOSCIENCE AND NANOTECHNOLOGY

TransPlatformer

We propose TransPlatformer for translating toxicogenomics from one platform to another. Transcriptomic profiling has evolved through multiple generations of technology, from microarrays (e.g., Affymetrix, CodeLink) to more recent high-throughput sequencing and targeted panels such as S1500+. Microarrays, which dominated gene expression studies in the early 2000s, provided affordable and high-throughput transcript quantification but suffered from cross-hybridization issues and limited dynamic range . RNA-Seq, introduced in the late 2000s, revolutionized transcriptomics by enabling unbiased and comprehensive gene expression analysis, albeit at higher costs and computational demands . Despite advances, many studies rely on historical microarray data, necessitating the translation of legacy data into modern platforms to ensure continuity and comparability. This translation is complicated by factors such as platform-specific probe design, differences in transcript coverage, and batch effects . Existing methods for cross-platform mapping include statistical normalization, machine learning models, and biological anchoring approaches. The ability to translate transcriptomic data between platforms has broad implications, including enhanced meta-analyses, improved toxicological modeling, and better integration of historical datasets with contemporary research. TransPlatformer seeks to contribute to this effort by evaluating translation methodologies and proposing novel strategies to improve cross-platform gene expression harmonization. In this repository there are code examples for TransPlatformer implementation

Cong, Guojing

Next generation retrofit wall panels with integrated vacuum insulation panels

Approximately two-thirds of residential buildings in the United States were constructed before the Department of Energy established energy conservation measures. These buildings present major opportunities for improving energy efficiency, though retrofitting them remains technically and economically challenging. This study presents the development and the durability evaluation of an innovative retrofit panel system that integrates vacuum insulation panels (VIP) with a nail-base panel (called a retrofit insulated panel) to enhance thermal performance with minimal disruption to occupants and without altering standard nail-based panel installation practices. Hygrothermal simulations were conducted to assess the moisture behavior of wall assemblies before and after retrofit installation under varying water vapor control strategies and climate conditions. Results indicate that, with appropriate moisture control strategy, the retrofit system effectively prevents moisture accumulation, keeping mold index values and relative humidity levels below critical thresholds. Additionally, Guarded Hot Box testing was performed to compute the effective R-value of the panel under different coverage areas that demonstrates its effectiveness in enhancing both thermal and moisture performance in existing residential buildings.

Iffa, Emishaw [ORNL]

DER Cybersecurity Standards: Assessment and Gap Analysis

The purpose of this report is to share the comprehensive gap analysis of existing cybersecurity standards applicable to Distributed Energy Resources (DERs) within the electric power sector. This analysis aims to identify critical deficiencies in current standards, assess their alignment with industry needs, and provide actionable recommendations for enhancing cybersecurity measures. The scope encompasses various DER technologies, including solar, wind, energy storage, and hydrogen fuel cells, and emphasizes the significance of establishing robust cybersecurity frameworks and standards to safeguard these increasingly integrated systems. The report provides valuable insights for stakeholders in the DER ecosystem, including manufacturers, utilities, and regulators. It underscores the importance of continued development and refinement of cybersecurity standards to keep up with the technical advances in DERs and associated cybersecurity challenges. The analysis evaluated IEC, IEEE, ISA, ISO, and UL standards relevant to DER cybersecurity. Standards were assessed on their coverage of key requirements including data availability, integrity, confidentiality, access control, authentication, encryption, and system hardening. For each standard, the analysis assessed its alignment with current industry practices, regulatory compliance, effectiveness in addressing known risks, coverage of emerging risks, and how it promotes interoperability. The evaluation also considered potential integration challenges and barriers to adoption.

97 MATHEMATICS AND COMPUTING

Selective Isolation of Surface Grain Boundaries by Oxide Dielectrics Improves Cd(Se,Te) Device Performance

Cd(Se,Te) photovoltaics (PV) are the most widely deployed thin-film solar technology globally, yet continued efficiency improvements are stymied by challenges at the device hole contacts. The inclusion of solution-processed oxide layers such as AlGaO x in the contact stack has yielded improved device open-circuit voltages (V OC ) and fill factors (FF). However, contradictory mechanisms by which these layers improve the device properties have been proposed by the research community. We demonstrate in this work that an underappreciated property of such spin-coated layers is the preferential deposition at grain boundaries, a process that isolates the grain boundaries during contact metallization. The effects of grain-boundary isolation are probed by varying the coverage of solution-processed AlGaO x “barrier” layers on the Cd(Se,Te) surface, quantified by scanning Auger microscopy. Examining coverage-dependent V OC and FF, it was observed that isolating the grain boundaries during metallization is sufficient to prevent damage to the absorber that occurs in devices lacking a barrier layer, while additional coverage contributes to the increased series resistance. Such an effect is agnostic to the material used as a barrier layer, as long as the material does not itself damage the absorber. Spin-coated SiO x was used in place of AlGaO x for an equally beneficial effect. This grain-boundary isolation phenomenon is also observed during Mo deposition and in absorbers that have been contacted with a nitrogen-doped ZnTe layer. The mechanisms by which metallization may degrade the absorber are discussed, as are contact design strategies leveraging barrier layers, which may lead to improved device efficiencies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Buried Interfaces in Organic Photocathodes for H 2 Evolution: Fermi-Level Pinning and Recombination

Herein, we demonstrate how Fermi-level pinning at buried contacts impacts solar fuel generation in all-polymer photocathodes by systematically comparing the effects of work function, hydroxyl coverage, and hydrogen evolution using chemically modified indium tin oxide (ITO) supports. Photovoltages and net photocathode performance are improved when the ITO is passivated using phosphonic acids, independent of work function, suggesting that the passivation reduces Fermi-level pinning at the buried interface arising from blended heterojunction interactions with surface metal hydroxyls. Transient photovoltage decay reveals differences in recombination mechanisms, supported by light intensity-dependent measurements. Briefly, nonpassivated, hydrophilic contacts exhibit trap-assisted recombination, while passivated, hydrophobic contacts follow bimolecular recombination. We then investigate changes in electroactivity of hole-transfer processes as a function of scan rate and repetitive cycling using a diffusion-controlled molecular redox probe, analogous to a hole-only device achieved via the electrolyte. The nonpassivated buried contacts exhibit higher overpotentials for oxidation, indicative of hole injection/extraction barriers. We observe irreversible electron transfer via the hole-transport level of the blended heterojunction and a strong cycle dependence, consistent with changes in the hole trap state density. Passivation results in more reversible redox behaviors, consistent with more Ohmic-like contacts. Collectively, these results provide context toward the realization of durable organic photoelectrodes with optimized photovoltages and net solar-to-hydrogen conversion efficiencies via fundamental understanding of the rates of carrier generation, recombination, and transport in high-dielectric aqueous environments and opportunities to characterize buried interfaces under device-relevant electric fields.

buried interfaces

PERSIANN-Unet: A Global Deep Learning Framework for Near-Real-Time Precipitation Estimation Using Infrared Data

Access to high-quality, high-resolution, near-real-time precipitation data is essential for hydrological and meteorological research and disaster mitigation. Traditional tools such as rain gauges and radar networks, though effective, have limitations, including sparse coverage in remote areas and high operational costs. Satellite data, with its global coverage and high spatial and temporal resolutions, mitigates limitations in coverage. Satellite precipitation products like Hydro Estimator (HE), Integrated Multi-satellitE Retrievals for Global Precipitation Measurement (IMERG), and Precipitation Estimation from Remotely Sensed Information using Artificial Neural Networks (PERSIANN) utilize both geosynchronous thermal infrared (IR) and passive microwave (PMW) data in their operation. PMW sensors offer detailed atmospheric profiles but suffer from higher latency, whereas IR sensors provide lower latency but only capture cloud-top information. Despite this constraint, IR data remains attractive for low-latency precipitation estimation. Recent advances in deep learning, particularly convolutional neural networks (CNNs), have further improved satellite precipitation retrievals. This study introduces PERSIANN-Unet (PUnet or PERSIANN V3), a quasi-global algorithm covering 60°N–60°S that combines IR data, monthly climatology, and the UNet architecture to produce half-hourly precipitation estimates at 0.04° resolution. The product is evaluated against HE, IMERG, and PDIR-Now for 2022–2023. Results show that PUnet closely matches its training target, IMERG V07 Final, at the global scale, and performance is further evaluated against Stage IV as a reference over CONUS. Training PUnet on IMERG (2016–2021) leverages a high-quality, integrated PMW IR-gauge precipitation product while developing an IR-based framework not reliant on PMW availability. By operating on a single global image, PUnet avoids tile partitioning and blending steps, reducing edge discontinuities, and produces more spatially consistent precipitation fields across hemispheres.

Phu Nguyen