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At least 613 records · Page 34

Alkali-induced catalytic tuning at metal and metal oxide interfaces

Alkali metals have been recognized as effective promoters in heterogeneous catalysis, capable of enhancing catalytic activity and tuning product distributions. Over the past few decades, significant efforts have been made aiming to reveal the mechanisms underlying the promoting effect of alkalis. However, the roles that alkali metals play in the catalytic process remain elusive due to challenges in capturing their catalytic behaviours upon exposure to reactive environments. This review summarizes recent surface science and theoretical studies of alkali (potassium, cesium)-decorated metal and metal oxide model catalysts, revealing the crucial tuning by alkalis of activity and selectivity for CO 2 hydrogenation. The analysis of electronic structures identifies the selective binding mechanism of the positively charged alkali ions on the surface, being able to reduce the surface work function and lead to strong electron polarization on the surfaces. Depending on the alkali–support interaction, the deposition of alkalis can selectively modify the bindings of reaction intermediates involved in CO 2 hydrogenation via the interplay among the ionic, covalent and electrostatic tunings. As a result, CO 2 can be effectively activated and converted into diverse products at the alkali–support interface, ranging from formic acid to methanol and ethanol. The identified selective bond-tuning advances the application of alkalis in promoting catalytic activity and controlling catalytic selectivity at alkali–support interfaces.

03 NATURAL GAS↗

Determination of latent dimensionality in international trade flow

Currently, high-dimensional data is ubiquitous in data science, which necessitates the development of techniques to decompose and interpret such multidimensional (aka tensor) datasets. Finding a low dimensional representation of the data, that is, its inherent structure, is one of the approaches that can serve to understand the dynamics of low dimensional latent features hidden in the data. Moreover, decomposition methods with non-negative constraints are shown to extract more insightful factors. Nonnegative RESCAL is one such technique, particularly well suited to analyze self-relational data, such as dynamic networks found in international trade flows. Particularly, non-negative RESCAL computes a low dimensional tensor representation by finding the latent space containing multiple modalities. Furthermore, estimating the dimensionality of this latent space is crucial for extracting meaningful latent features. Here, to determine the dimensionality of the latent space with non-negative RESCAL, we propose a latent dimension determination method which is based on clustering of the solutions of multiple realizations of non-negative RESCAL decompositions. We demonstrate the performance of our model selection method on synthetic data. We then apply our method to decompose a network of international trade flows data from International Monetary Fund and shows that with a correct latent dimension determination, the resulting features are able to capture relevant empirical facts from economic literature.

97 MATHEMATICS AND COMPUTING↗

Light regulation of light-harvesting antenna size substantially enhances photosynthetic efficiency and biomass yield in green algae

One of the major factors limiting biomass productivity in algae is the low thermodynamic efficiency of photosynthesis. The greatest thermodynamic inefficiencies in photosynthesis occur during the conversion of light into chemical energy. At full sunlight the light-harvesting antenna captures photons at a rate nearly 10 times faster than the rate-limiting step in photosynthetic electron transport. Excess captured energy is dissipated by non-productive pathways including the production of reactive oxygen species. Substantial improvements in photosynthetic efficiency have been achieved by reducing the optical cross-section of the light-harvesting antenna by selectively reducing chlorophyll b levels and peripheral light-harvesting complex subunits. Smaller light-harvesting antenna, however, may not exhibit optimal photosynthetic performance in low or fluctuating light environments. Additionally, we describe a translational control system to dynamically adjust light-harvesting antenna sizes for enhanced photosynthetic performance. Furthermore, by expressing a chlorophyllide a oxygenase (CAO) gene having a 5' mRNA extension encoding a Nab1 translational repressor binding site in a CAO knockout line it was possible to continuously alter chlorophyll b levels and correspondingly light-harvesting antenna sizes by light-activated Nab1 repression of CAO expression as a function of growth light intensity. Significantly, algae having light-regulated antenna sizes had substantially higher photosynthetic rates and two-fold greater biomass productivity than the parental wild-type strains as well as near wild-type ability to carry out state transitions and non-photochemical quenching. These results have broad implications for enhanced algae and plant biomass productivity.

09 BIOMASS FUELS↗

Sound Speed as a Candidate for Internal Temperature Monitoring During Solid Phase Processing of Materials

Internal temperature is an important parameter for understanding the solid phase processing (SPP) of materials and improving feedback control of these processes. Friction stir processes, shear assisted processing and extrusion (ShAPE ™ ), and ultrahigh velocity (UHV) cold spray are examples of such processes. Simple thermal models based on temperatures measured at the boundary of the deforming body cannot capture the dynamic nature of temperature generation within the deforming solid. One possibly way of understanding internal temperature is by measuring sound speed, which varies as a function of temperature for materials and directing ultrasonic wave propagation through selected material volumes of interest. In this project, longitudinal wave speed is estimated for aluminum 6061. Piezoelectric materials bonded to a specimen provided data from which longitudinal wave speed was estimated. A discussion evaluated the linear relationship of wave speed versus temperature and postulated how wave speed measurements could be used to estimate the internal temperature of selected material volumes for feedback during SPP of materials. Instrumentation, data and analysis, and a discussion are reviewed.

36 MATERIALS SCIENCE↗

Interfacial interactions between polymers and selective adsorbents influence ion transport properties of boron scavenging ion-exchange membranes

The recent emergence of adsorptive ion-exchange membranes (IEMs), designed by the synergistic integration of highly selective porous aromatic frameworks (PAFs) with ion-exchange polymers, has enabled simultaneous desalination and targeted removal of specific solutes (e.g., mercury, iron, boron, etc.). While the addition of highly selective PAFs to IEMs yields membranes with entirely new functions, PAF-polymer interactions, and the effects of such interactions on ion transport properties of the membranes, are not well understood. In this study, we developed cross-linked adsorptive cation- and anion-exchange membranes (CEMs and AEMs) for simultaneous desalination and boron removal via in-situ formation of the cross-linked polymer network around the boron selective PAF particles. Here we systematically investigated the influence of PAF loading level on PAF-polymer interactions as well as the equilibrium and transport properties of the adsorptive IEMs. The interactions between the PAF and the ion-exchange polymer matrix differed for the CEMs and AEMs due to differences in the fixed charge group chemistry. Notably, the sulfonate groups of the CEMs can form hydrogen bonds with the hydroxyl groups of the PAF, while the quaternary ammonium groups in the AEMs cannot. These differences in interfacial interactions did not significantly impact counter-ion transport across the adsorptive IEMs but had a significant influence on co-ion transport, which affected the counter-ion/co-ion selectivity of the membranes. The selectivity of the adsorptive CEMs decreased while that of the adsorptive AEMs increased with PAF loading level. The results of this study underscore the importance of controlling interfacial interactions when designing adsorptive IEMs for simultaneous water desalination and solute capture and recovery.

36 MATERIALS SCIENCE↗

Clicking the Surface of Poly[1-(trimethylsilyl)propyne] (PTMSP) via a Thiol–Ene Reaction: Unexpected CO 2 /N 2 Permeability

The surface modification of poly[1-(trimethylsilyl)- propyne] (PTMSP) film via a thiol-ene click reaction with sodium 3-mercapto-1-propanesulfonate has yielded membranes having a CO 2 permeance as high as 530 GPU with a CO 2 /N 2 selectivity of 21. This level of performance, together with the simplicity of this surface modification, indicates that such materials could become viable alternatives to some of the most enticing membrane materials that are currently being explored for the practical capture of CO 2 from flue gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transparent window 2D IR spectroscopy of proteins

Proteins are complex, heterogeneous macromolecules that exist as ensembles of interconverting states on a complex energy landscape. A complete, molecular-level understanding of their function requires experimental tools to characterize them with high spatial and temporal precision. Infrared (IR) spectroscopy has an inherently fast time scale that can capture all states and their dynamics with, in principle, bond-specific spatial resolution. Two-dimensional (2D) IR methods that provide richer information are becoming more routine but remain challenging to apply to proteins. Spectral congestion typically prevents selective investigation of native vibrations; however, the problem can be overcome by site-specific introduction of amino acid side chains that have vibrational groups with frequencies in the “transparent window” of protein spectra. This Perspective provides an overview of the history and recent progress in the development of transparent window 2D IR of proteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microbial β-glucuronidases drive human periodontal disease etiology

Periodontitis is a chronic inflammatory disease associated with persistent oral microbial dysbiosis. The human β-glucuronidase (GUS) degrades constituents of the periodontium and is used as a biomarker for periodontitis severity. However, the human microbiome also encodes GUS enzymes, and the role of these factors in periodontal disease is poorly understood. Here, we define the 53 unique GUSs in the human oral microbiome and examine diverse GUS orthologs from periodontitis-associated pathogens. Oral bacterial GUS enzymes are more efficient polysaccharide degraders and processers of biomarker substrates than the human enzyme, particularly at pHs associated with disease progression. Using a microbial GUS-selective inhibitor, we show that GUS activity is reduced in clinical samples obtained from individuals with untreated periodontitis and that the degree of inhibition correlates with disease severity. Together, these results establish oral GUS activity as a biomarker that captures both host and microbial contributions to periodontitis, facilitating more efficient clinical monitoring and treatment paradigms for this common inflammatory disease.

59 BASIC BIOLOGICAL SCIENCES↗

NiAl–MoO 2 S 2 Nanoparticles: Structural Evolution and Mechanistic Insights into High-Performance Selenium Oxyanion Removal across Diverse pH Conditions

Advancing sorbent materials for the selective removal of toxic oxyanions from water requires synthetic control, tunable chemistry, and an atomic-level understanding of structure–function relationships. Here, we report the synthesis and detailed characterization of NiAl–MoO 2 S 2 , a novel layered double hydroxide (LDH) nanomaterial designed for the efficient sequestration of selenium oxoanions (SeO 3 2– and SeO 4 2– ) from complex aqueous environments. The material is synthesized through a room-temperature ion-exchange process, wherein interlayer NO 3 – anions in NiAl–LDH are replaced with MoO 2 S 2 2– clusters, forming high-surface-area, flower-like nanoparticles. Comprehensive structural analysis using the synchrotron X-ray pair distribution function, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy reveals a distinct chemical transformation of intercalated [MoO 2 S 2 ] 2– into [Mo 2 O 2 S 6 ] 2– -like clusters, generating redox-active interlayers that drive selenium capture. This tailored interfacial chemistry underpins the material’s exceptional sorption performance, achieving distribution coefficients (K d ) ≥ 10 6 mL/g and maximum capacities of 343 mg/g for SeO 4 2– and 514 mg/g for SeO 3 2– , outperforming state-of-the-art inorganic sorbents. Importantly, NiAl–MoO 2 S 2 maintains high selectivity and capacity across acidic, neutral, and alkaline pH, efficiently removing selenium from ppm to sub-10 ppb trace levels, even in the presence of competing ions typical of natural and industrial waters. The selenium uptake proceeds via reductive precipitation coupled with the oxidation of molybdenum and sulfide within the LDH framework. This study highlights the power of strategic synthetic modification and interlayer functionalization in LDHs to unlock new structural motifs and redox chemistries, offering a scalable route to advanced materials for environmental remediation.

Adsorption↗

Ground-motions site and event specificity: Insights from assessing a suite of simulated ground motions in the San Francisco Bay Area

This article presents the results of a research that is part of a larger collaborative effort between the Lawrence Berkeley National Laboratory and the Pacific Earthquake Engineering Research Center, funded by the US Department of Energy Office of Cybersecurity, Energy Security and Emergency Response. The main objective of this study is to assess a suite of near and far-field simulated ground motions obtained from 20 realizations of an M7 Hayward Fault earthquake in the San Francisco Bay Area, California USA, and inform the selection of rupture simulation parameters leading to strong motions. To this aim, comparisons are conducted with NGA-W2 and directivity ground-motion models and a selected population of records. An archetypal steel moment-resisting frame is utilized to assess infrastructure response distributions. The analyses carried out for each simulated event and subdomain with consistent properties in terms of shallow shear-wave velocity proved to be instrumental for better interpreting the differences between simulated motions and empirical models. The main reasons identified for variances between simulations and empirical relationships included (1) directivity effects fully captured by the simulations across the full breadth of rupture models; (2) site vicinity to ruptures that incorporate large-slip patches, particularly if these are in the forward-directivity direction; and (3) presence of geologic structures that can “trap” seismic waves and produce ground motions with large amplitude and long signal duration. The analyses carried out in this work provide a path for interpreting ground-motion site and event specificity obtained from a suite of physics-based simulations, differing only in the rupture model characterization, to inform the selection of simulation scenarios for site-specific engineering analyses under strong excitations. Evidence from this work points to the possibility that current hazard models may underestimate ground-motion intensities in areas where the combined effect of directivity and site conditions results in large ground-motion amplitudes.

58 GEOSCIENCES↗

Experimental uncertainty quantification using templates of expected measurement uncertainties for fast neutron-induced total, capture, and scattering cross sections

Careful experimental uncertainty quantification (UQ) is key for developing trustworthy evaluated nuclear data. Templates to account for missing or under-reported experimental uncertainties were recently developed by the covariance committee of Cross Section Evaluation Working Group (CSEWG). In this work, we illustrate the practical application and limitations of these templates for selected neutron-induced reactions, including (n, tot), (n, γ), and (n, xn) in the fast energy range, to illustrate their use in data analyses for nuclear data evaluations. We show that while the templates provide consistent framework, proper implementation still requires detailed knowledge of experimental conditions and careful treatment of nonlinear effects in cross section derivation. Case studies highlight how template-assisted UQ improves consistency with previous evaluations such as ENDF/B and reveals open challenges in propagating uncertainties across different energy regimes. The main contribution of this paper is to connect formal template recommendations with their use in practical evaluation workflows, clarifying both their benefits and current limitations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Improving energy yield in photovoltaic modules with photonic structures

When installed outdoors, Si solar cells typically operate 20 – 30 K above ambient conditions. These elevated operating temperatures lead to diminished performance, reducing efficiency by ~0.4%/K for crystalline Si cells and decreasing module lifetime. Since much of the elevated temperature of the modules derives from parasitic absorption of sub-bandgap sunlight by the contacts, encapsulants, or other materials, reflectors that remove the sub-bandgap radiation from the module before it is absorbed promise to reduce the operating temperature. However, there are many competing strategies to reject this light: selective reflectors could be integrated into the outer module glass, at the textured Si-encapsulant interface, or on the rear. Furthermore, many of these approaches are complex and expensive to fabricate. The issue of heating can be even more critical in bifacial modules: high fractions of rear irradiance can lead to higher operating temperatures. Prior to this project, relatively little was known about the optical strategies for temperature reduction in bifacial modules. The goal of this project was to quantitatively assess optical strategies for improving the energy yield via a combination of improved anti-reflection and sub-bandgap light rejection. We studied two complementary concepts: the performance of ideal structures to determine the upper limits to performance, and low-complexity structures made from standard materials as cost-effective implementations. We also studied the performance of these reflectors in different types of modules, including Al BSF, PERC, and bifacial. Here we build from our prior accomplishments in developing mirror optimization techniques, and make use of simulation methods that accurately capture the optical properties of the modules throughout the visible and near-infrared spectrum. We connect these optical properties to energy yield under realistic, outdoor conditions. We also experimentally fabricated mirrors, incorporated them into mini-modules, and performed outdoor testing of performance at NREL. We found definitively that spectrally-selective mirrors on the outside of the module cover glass offer the best performance, both under ideal conditions and for realistic, low- complexity mirrors. Mirrors at the Si cell/encapsulant interface are limited by the multiple reflections needed to remove sub-bandgap light. Mirrors at the cell surface and mirrors on the rear also cannot remove all the sub-bandgap light, since parasitic absorption also occurs in the cover glass, encapsulant, and front contacts, depending on the module configuration. Also, cell texturing places higher demands on any cell-surface mirror because multiple interactions with the mirror are required to reject sub bandgap light which compounds losses. For bifacial modules, mirrors on the back do provide additional cooling and energy yield improvements, and the mirrors can have the same structure. In the monofacial case up to 3.3K of cooling is possible for mirrors on the front, compared to 2.2K at the cell surface and 1.2K at the rear. For bifacial modules, up to 2.4K of cooling is possible when mirrors are included at both the front and back. Our realistic designs utilize 4 – 6 layers of common photovoltaic materials such as SiO 2 , TiO 2 , and SiN x , making them more cost effective. Finally, we used our models to study thermal management in bifacial modules with different back lamination materials, finding that glass-glass laminated modules operated hotter than equivalent glass-polymer backsheet modules, due solely to the increased absorption of light incident from the rear of the module. Improving the energy yield by 2%, which is achievable with these realistic designs, would lead to LCOE reductions of $0.03/kWh by 2030. These benefits make photovoltaic panels more accessible to the public and may reduce associated maintenance costs.

14 SOLAR ENERGY↗

Novel in-capsule synthesis of metal–organic framework for innovative carbon dioxide capture system

Metal-Organic Frameworks (MOFs) have been developed as solid sorbents for CO2 capture applications and their properties can be controlled by tuning the chemical blocks of their crystalline units. A number of MOFs (e.g., HKUST-1) have been developed but the question remains how to deploy them for gas–solid contact. Unfortunately, the direct use of MOFs as nanocrystals would lead to serious problems and risks. Here, for the first time, we report a novel MOF-based hybrid sorbent that is produced via an innovative in-situ microencapsulated synthesis. Using a custom-made double capillary microfluidic assembly, double emulsions of the MOF precursor solutions and UV-curable silicone shell fluid are produced. Subsequently, HKUST-1 MOF is successfully synthesized within the droplets enclosed in the gas permeable microcapsules. The developed MOF-bearing microcapsules uniquely allow the deployment of functional nanocrystals without the challenge of handling ultrafine particles, and further, can selectively reject undesired compounds to protect encapsulated MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluating the benefits of kinetic Monte Carlo and microkinetic modeling for catalyst design studies in the presence of lateral interactions

Popular computational catalyst design strategies rely on the identification of reactivity descriptors, which can be used along with Brønsted–Evans–Polanyi (BEP) and scaling relations as input to a microkinetic model (MKM) to make predictions for activity or selectivity trends. The main benefit of this approach is related to the inherent dimensionality reduction of the large material space to just a few catalyst descriptors. Conversely, it is well documented that a small set of descriptors is insufficient to capture the intricacies and complexities of a real catalytic system. The inclusion of coverage effects through lateral adsorbate-adsorbate interactions can narrow the gap between simplified descriptor predictions and real systems, but mean-field MKMs cannot properly account for local coverage effects. This shortcoming of the mean-field approximation can be rectified by switching to a lattice-based kinetic Monte Carlo (kMC) method using cluster expansion representation of adsorbate–adsorbate lateral interactions. Using the prototypical CO oxidation reaction as an example, we critically evaluate the benefits of kMC over MKM in terms of trend predictions and computational cost when using only a small set of input parameters. After confirming that in the absence of lateral interactions the kMC and MKM approaches yield identical trends and mechanistic information, we observed substantial differences between the two kinetic models when lateral interactions were introduced. Here, the mean-field implementation applies coverage corrections directly to the descriptors, causing an artificial overprediction of the activity of strongly binding metals. In contrast, the cluster expansion in kMC implementation can differentiate among the highly active metals but it is very sensitive to the set of included interaction parameters. Considering that computational screening relies on a minimal set of descriptors, for which MKM makes reasonable trend predictions at a ca. three orders of magnitude lower computational cost than kMC, the MKM approach does provide a better entry point for computational catalyst design.

36 MATERIALS SCIENCE↗

Dynamic study of direct CO 2 capture from indoor air using poly(ethylenimine)-impregnated fiber sorbents

Supported amine adsorbents are promising materials for direct air capture (DAC) of CO 2 due to their high CO 2 capacity and relatively low energy requirement for regeneration. For a DAC process, it is essential to properly define operating parameters to achieve high sorbent productivity (amount of CO 2 captured per unit quantity of sorbent material over unit time). It is furthermore essential to understand the kinetic behavior of the process under the influence of various operating conditions such as the inlet air velocity, sorbent composition, and humidity to select an effective range of operating conditions to maximize sorbent productivity. Here, the dynamic behavior of a DAC process is probed using a fixed fiber sorbent contactor containing poly(ethylenimine) (PEI)-impregnated composite silica/cellulose acetate (CA) fibers. Throughout this study, experiments are conducted using both simulated air (398 ppm CO 2 balanced by N 2 ) and real indoor air (~400–500 ppm CO 2 ). The experimental behavior of the fibers using simulated air and indoor air is compared, and the influence of the inlet air velocity on the breakthrough behavior is assessed. By changing operating conditions, the impact on the fiber sorbent productivity (mmol CO 2 g fiber –1 h –1 ) is quantified to identify conditions that could favor high rates of CO 2 removal. The kinetics of steam-assisted CO 2 desorption are studied, identifying achievable desorption times. Productivities of 1.2 mmol CO 2 g fiber –1 h –1 are obtained using an inlet air velocity of 1.1 m s –1 . Performance trends show that further increasing the inlet air velocity will likely lead to even higher productivities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-molecule infrared spectroscopy with scanning tunneling microscopy

Probing vibrations at the single-molecule level is essential for achieving bond-specific chemical control in realistic heterogeneous environments. Here, we introduce a new measurement scheme that integrates frequency-tunable infrared excitation with scanning tunneling microscopy to characterize vibration-mediated nuclear motions of single molecules. We first validated the technique by monitoring the infrared-induced rotation of the ethynyl radical and then applied it to mapping pyrrolidine’s conformational dynamics. The resulting broadband spectra captured fundamental vibrational modes together with rich overtone and combination bands inaccessible by conventional methods, which we confirmed with isotopic substitutions. Density functional theory calculations showed that delocalized modes coupled with pyrrolidine ring puckering drive the structural transition, revealing altered selection rules compared with traditional infrared spectroscopy. Here, this new experimental platform enables molecular vibrations and transformations to be probed with atomic precision.

Liang, Kangkai [University of California, San Dieg↗

Cosmic Ray Mediated Thermal Fronts in the Warm-Hot Circumgalactic Medium

We investigate the 1D plane-parallel front connecting the warm ($10^4$ K) and hot ($10^6$ K) phases of the circumgalactic medium (CGM), focusing on the influence of cosmic rays (CRs) in shaping these transition layers. We find that cosmic rays dictate the thermal balance while other fluxes (thermal conduction, radiative cooling, and gas flow) adjust to compensate. We compute column density ratios for selected transition temperature ions and compare them with observational data. While most of our models fail to reproduce the observations, a few are successful, although we make no claims for their uniqueness. Some of the discrepancies may indicate challenges in capturing the profiles in cooler, photoionized regions, as has been suggested for by previous efforts to model thermal transition layers.

79 ASTRONOMY AND ASTROPHYSICS↗

Field-Scale Testing of a High-Efficiency Membrane Reactor (MR)—Adsorptive Reactor (AR) Process for H2 Generation and Pre-Combustion CO2 Capture

The study objective was to field-validate the technical feasibility of a membrane- and adsorption-enhanced water gas shift reaction process employing a carbon molecular sieve membrane (CMSM)-based membrane reactor (MR) followed by an adsorptive reactor (AR) for pre-combustion CO2 capture. The project was carried out in two different phases. In Phase I, the field-scale experimental MR-AR system was designed and constructed, the membranes, and adsorbents were prepared, and the unit was tested with simulated syngas to validate functionality. In Phase II, the unit was installed at the test site, field-tested using real syngas, and a technoeconomic analysis (TEA) of the technology was completed. All project milestones were met. Specifically, (i) high-performance CMSMs were prepared meeting the target H2 permeance (>1 m3/(m2.hbar) and H2/CO selectivity of >80 at temperatures of up to 300 °C and pressures of up to 25 bar with a <10% performance decline over the testing period; (ii) pelletized adsorbents were prepared for use in relevant conditions (250 °C < T < 450 °C, pressures up to 25 bar) with a working capacity of >2.5 wt.% and an attrition rate of <0.2; (iii) TEA showed that the MR-AR technology met the CO2 capture goals of 95% CO2 purity at a cost of electricity (COE) 30% less than baseline approaches.

42 ENGINEERING↗