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At least 397 records · Page 22

Highly efficient semi-hydrogenation in strained ultrathin PdCu shell and the atomic deciphering for the unlocking of activity-selectivity

Excellent ethylene selectivity in acetylene semi-hydrogenation is often obtained at the expense of activity. To break the activity-selectivity trade-off, precise control and in-depth understanding of the three-dimensional atomic structure of surfacial active sites are crucial. Here, we designed a novel Au@PdCu core–shell nanocatalyst featuring diluted and stretched Pd sites on the ultrathin shell (1.6 nm), which showed excellent reactivity and selectivity, with 100% acetylene conversion and 92.4% ethylene selectivity at 122 °C, and the corresponding activity was 3.3 times higher than that of the PdCu alloy. The atomic three-dimensional decoding for the activity-selectivity balance was revealed by combining pair distribution function (PDF) and reverse Monte Carlo simulation (RMC). The results demonstrate that a large number of active sites with a low coordination number of Pd–Pd pairs and an average 3.25% tensile strain are distributed on the surface of the nanocatalyst, which perform a pivotal function in the simultaneous improvement of hydrogenation activity and ethylene selectivity. Our work not only develops a novel strategy for unlocking the linear scaling relation in heterogeneous catalysis but also provides a paradigm for atomic 3D understanding of lattice strain in core–shell nanocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of size and structure of catalytic active sites in polyolefin hydrogenolysis

The increasing amount of plastic waste poses serious environmental problems that threaten both ecosystems and human well-being. Hydrogenolysis has been widely studied as an effective approach for converting polyolefins into high-value liquids and waxy fuels. Their multifaceted reaction mechanism, including dehydrogenation, C–C bond cleavage, and hydrogenation, highlights the need for sophisticated catalyst design. The suppression of methane production, a persistent challenge in polyolefin hydrogenolysis, requires precise control of the cleavage site and inhibition of successive C–C bond cleavage. This delicate balance is achieved by carefully tuning the size and structure of metals. In this review, we investigate the effects of the size and structure of active sites on their catalytic activity and selectivity for the hydrogenolysis of polyolefins, including polyethylene and polypropylene. In conclusion, a fundamental understanding of hydrogenolysis mechanisms, combined with strategic synthetic methodologies, is crucial for creating efficient catalysts with tailored properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural basis for divergent C–H hydroxylation selectivity in two Rieske oxygenases

Biocatalysts that perform C–H hydroxylation exhibit exceptional substrate specificity and site-selectivity, often through the use of high valent oxidants to activate these inert bonds. Rieske oxygenases are examples of enzymes with the ability to perform precise mono- or dioxygenation reactions on a variety of substrates. Understanding the structural features of Rieske oxygenases responsible for control over selectivity is essential to enable the development of this class of enzymes for biocatalytic applications. Decades of research has illuminated the critical features common to Rieske oxygenases, however, structural information for enzymes that functionalize diverse scaffolds is limited. Here, we report the structures of two Rieske monooxygenases involved in the biosynthesis of paralytic shellfish toxins (PSTs), SxtT and GxtA, adding to the short list of structurally characterized Rieske oxygenases. Based on these structures, substrate-bound structures, and mutagenesis experiments, we implicate specific residues in substrate positioning and the divergent reaction selectivity observed in these two enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Defect-mediated diffusion of implanted Mg in GaN: Suppressing dopant redistribution by sequential thermal and microwave annealing

The diffusion behavior of Mg in Mg/N co-implanted GaN is investigated in response to a set of annealing conditions and methodologies, namely, 1000 °C/30 min thermal anneal, by high-temperature pulsed gyrotron microwave annealing at 1420 or 1500 °C, or by thermal and microwave annealing, sequentially. After 1000 °C annealing, the diffusion of Mg in GaN is found to be negligible, as measured by secondary ion mass spectrometry. Annealing by gyrotron microwave annealing alone induces the diffusion of Mg at a rate on the order of 10 −12 cm 2 /s. However, the use of a thermal anneal before microwave gyrotron annealing reduces this rate by an order of magnitude to 10 −13 cm 2 /s. We find that a model that considers Mg diffusion from an inhomogeneous medium that contains a defect-rich implanted region near-surface to a relatively pristine region below the implant range better explains the observed diffusion behavior than a conventional model that assumes a homogeneous medium. By analyzing the diffusion behavior using the Boltzmann–Matano method, we present a discussion of reduction in [V Ga ] by thermal annealing at 1000 °C, leading to a suppressed diffusion coefficient during subsequent high-temperature annealing relative to diffusion after 1420/1500 °C annealing alone. This effect holds potential for improvement in the precision of selectively doped regions for future applications based on the (Al)GaN material system. An improved field profile control in real devices can increase the breakdown and current-handling capabilities in power electronic applications.

Meyers, V.↗

Mid-infrared spectroscopy with a broadly tunable thin-film lithium niobate optical parametric oscillator

Mid-infrared spectroscopy, an important technique for sensing molecules, has encountered barriers from sources either limited in tuning range or excessively bulky for widespread use. We present a compact, efficient, and broadly tunable optical parametric oscillator surmounting these challenges. Leveraging dispersion-engineered thin-film lithium niobate-on-sapphire photonics and a singly resonant cavity allows broad, controlled tuning over an octave from 1.5–3.3 µm. The device generates >25mW of mid-infrared light at 3.2 µm with 15% conversion efficiency. The ability to precisely control the device’s mid-infrared emission enables spectroscopy of methane and ammonia, demonstrating our approach’s relevance for sensing. Our work signifies an important advance in nonlinear photonics miniaturization, bringing practical field applications of high-speed, broadband mid-infrared spectroscopy closer to reality.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Use of Lignin-Based Admixture as Water Reducer (WRA) for Tailoring the Rheological Properties of Mortars for 3D-Printing

Efforts towards decarbonizing construction materials and industrial processes related to cement and concrete can be aided via multifaceted approaches that target alternative admixtures as well as precision control of fabrication. Chemical admixtures for water reduction have played a crucial role in the development of advanced mortar and concrete mixtures. Newer biomass processing techniques developed for aviation fuel production from corn stover biomass produce a highly reactive lignin byproduct that is suitable for chemical modifications to mimic the properties of commonly used polycarboxylate ethers (PCEs) with a smaller carbon footprint. These lignin-based plasticizers developed at NREL can be used in place of petrochemical-derived superplasticizers to tailor the rheological properties of cement-based systems for applications such as additive manufacturing while reducing the carbon intensity of the concrete mix. Lignosulfonates derived from paper pulping were historically used as water reducers only to be displaced with the rise of PCEs. The present study examines the use of a NREL produced lignin-based water reducing admixture (WRA), in cement pastes and mortar mixtures for 3D-printing at small- (mm) scale. The experimental program consisted of different formulations of oxidized lignin-based WRAs added in variable dosages to cement pastes with a fixed water-to-cement ratio. The objective is to achieve an appropriate workability, extrudability and buildability of mortar mixtures to produce 3D-printed specimens. The rheological characterization was performed to compare the initial yield stress and viscosity of the different mixtures with lignin-based admixture with respect to conventional PCE superplasticizers. The rheological characterization shows that the proposed material act as an effective water-reducer in cement systems, affecting the yield stress, plastic viscosity, and structuration rate of the mixtures evaluated. On the other hand, the effect on early hydration process of the cement pastes containing lignin-based admixtures is comparable to conventional superplasticizers.

3D-printing↗

Reliability, biological variability, and accuracy of multi-frequency bioelectrical impedance analysis for measuring body composition components

Introduction Bioelectrical impedance analysis (BIA) systems are gaining popularity for use in research and fitness assessments as the technology improves and becomes more affordable and easier to use. Multifrequency BIA (MF-BIA) may improve accuracy and precision using octopolar contacts for segmental analyses. Purpose Evaluate reliability, biological variability, and accuracy of component measures (total body water, mass, and composition) of commercially available MF-BIA system (InBody 770, Cerritos, California, USA). Methods Fourteen healthy military-age adults were assessed by MF-BIA in duplicate on five laboratory visits across 3 weeks (10 measures each). Participants were evaluated at the same time of day after refraining from strenuous exercise (> 48 h), alcohol consumption (> 24 h), and caffeine, nicotine, and food (> 10 h). Systematic error (test–retest reliability) and biological variability (day-to-day reliability) were summarized by intraclass correlation coefficient (ICC) values determined for body mass (fat, fat-free, total) and body water (extracellular, intracellular, total). Body composition measurements derived from BIA on the second visit were also tested for accuracy compared to dual-energy x-ray absorptiometry (DXA). Results Test–retest reliability was very high for all measurements of whole-body water and mass (ICC ≥ 0.999) and high for regional body water and mass (ICC 0.973–1.000). Biological variability was observable with very minor differences between tests (same day) for total and regional body water (0.0–0.2 L) and total and regional body mass measurements (0.0–0.2 kg); while between day differences were slightly higher (0.0–0.5 L and 0.1–0.7 kg). Compared to DXA, the MF-BIA whole-body measures showed an offset in %BF (Bias −4.0 ± 2.8%; Standard error of the estimate (SEE), 2.6%), an overprediction for total body fat-free mass (Bias 2.8 ± 2.1 kg; SEE 2.2 kg) and an underprediction of total body fat mass (Bias −2.9 ± 2.0 kg; SEE 1.9 kg). Conclusion Under controlled conditions with fit and healthy men and women, this MF-BIA system has high methodological reliability and demonstrates stable day-to-day measurements of major body composition components. Previously reported ~3% body fat offset compared to criterion methods was again confirmed. Precision of the InBody 770 shows consistency and supports further testing of this specific device as a new military standards method and suitability across a wider range of %BF.

Nutrition & Dietetics↗

Loschmidt-echo approach to error estimation in Krylov-subspace approximation

The Krylov subspace method is a traditional approach to approximate quantum evolution, allowing us to treat systems with large Hilbert spaces. Despite its popularity, current bounds typically overestimate the error, which translates into more expensive simulation routines. Here, in this paper, we tackle this problem by realizing that the error can be understood as a Loschmidt echo in a one-dimensional (1D) noninteracting tight-binding Hamiltonian. We show that the different time regimes of the approximation can be understood using simple physical ideas. More importantly, we obtain computationally cheap error bounds that describe with high precision the actual error in the approximation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A Self-Organizing Nano Grid (SONG) for Energy Access Clusters

In this paper, a bottom-up dc Self-Organizing Nano Grid (SONG) for rural electrification at ultra-low-cost through a flexible and scalable topology is presented. The proposed nano grid requires no communication and uses dc-bus signaling to convey excess energy in the system through the bus voltage, allowing independent agents to conduct energy transactions based on their needs in a decentralized manner. Moreover, this article proposes a concept that uses a novel multi-source, multi-segment droop control strategy with demand coordination, allowing for dynamic self-balancing of the system under fluctuating operating conditions. The unique use of a surplus photovoltaic (PV) power droop mode precisely estimates energy availability to minimize load chattering that helps in stabilizing the dc-bus. In addition, this architecture uses standard dc/dc converters for a low-cost, modular, Plug and Play ( PnP ) solution with highly automated operation, enabling local assembly, operation, and maintenance by non-technical personnel. The proposed SONG concept was validated in simulation and with a 700W, laboratory-scale, custom made nano grid system. The simulation and experimental test cases show the feasibility of the SONG system by demonstrating the proposed multi-source, multi-segment droop control strategy without load chattering under varying operating conditions.

dc-dc converter↗

Dynamic and static corrosion of chromium-alumina refractory in simulated nuclear waste glass

Monofrax® K-3, a chromium–alumina refractory, is widely used in nuclear waste glass melters due to its high durability. However, aggressive vitrification conditions still lead to corrosion that limits melter lifespan. Here, this study investigates two key corrosion modes, subsurface and melt-line corrosion, under static and dynamic conditions, using a custom setup enabling precise control of melt velocity and temperature. Experimental results, interpreted using diffusion-limited dissolution models, show that (i) subsurface corrosion increases by approximately 10% per mm/s increase in melt velocity, while melt-line corrosion remains virtually unaffected, (ii) corrosion rate dependence on temperature is inversely proportional to melt viscosity, and (iii) glass composition affects both corrosion modes similarly, based on Cr 2 O 3 , Al 2 O 3 , and alkali contents. The experimental data also allowed the determination of diffusion coefficients of major dissolving species, which were found to be consistent between the melt-line and subsurface corrosion models, indicating their suitability for future CFD studies.

12 - MGMT OF RADIOACTIVE AND NON-RADIOACTIVE WASTE↗

Machine-learning based prediction of injection rate and solenoid voltage characteristics in GDI injectors

We report that current state-of-the-art gasoline direct-injection (GDI) engines use multiple injections as one of the key technologies to improve exhaust emissions and fuel efficiency. For this technology to be successful, secured adequate control of fuel quantity for each injection is mandatory. However, nonlinearity and variations in the injection quantity can deteriorate the accuracy of fuel control, especially with small fuel injections. Therefore, it is necessary to understand the complex injection behavior and to develop a predictive model to be utilized in the development process. This study presents a methodology for rate of injection (ROI) and solenoid voltage modeling using artificial neural networks (ANNs) constructed from a set of Zeuch-style hydraulic experimental measurements conducted over a wide range of conditions. A quantitative comparison between the ANN model and the experimental data shows that the model is capable of predicting not only general features of the ROI trend, but also transient and non-linear behaviors at particular conditions. In addition, the end of injection (EOI) could be detected precisely with a virtually generated solenoid voltage signal and the signal processing method, which applies to an actual engine control unit. A correlation between the detected EOI timings calculated from the modeled signal and the measurement results showed a high coefficient of determination.

42 ENGINEERING↗

Wetting transition and fluid trapping in a microfluidic fracture

Immiscible fluid–fluid displacement in confined geometries is a fundamental process occurring in many natural phenomena and technological applications, from geological CO 2 sequestration to microfluidics. Due to the interactions between the fluids and the solid walls, fluid invasion undergoes a wetting transition from complete displacement at low displacement rates to leaving a film of the defending fluid on the confining surfaces at high displacement rates. While most real surfaces are rough, fundamental questions remain about the type of fluid–fluid displacement that can emerge in a confined, rough geometry. Here, we study immiscible displacement in a microfluidic device with a precisely controlled structured surface as an analogue for a rough fracture. We analyze the influence of the degree of surface roughness on the wetting transition and the formation of thin films of the defending liquid. We show experimentally, and rationalize theoretically, that roughness affects both the stability and dewetting dynamics of thin films, leading to distinct late-time morphologies of the undisplaced (trapped) fluid. Finally, we discuss the implications of our observations for geologic and technological applications.

42 ENGINEERING↗

Quantum advantages for Pauli channel estimation

We show that entangled measurements provide an exponential advantage in sample complexity for Pauli channel estimation, which is both a fundamental problem and a practically important subroutine for benchmarking near-term quantum devices. The specific task we consider is to simultaneously learn all the eigenvalues of an n-qubit Pauli channel to ±ε precision. We give an estimation protocol with an n-qubit ancilla that succeeds with high probability using only O(n/ε 2 ) copies of the Pauli channel, while proving that any ancilla-free protocol (possibly with adaptive control and channel concatenation) would need at least Ω(2 n/3 ) rounds of measurement. We further study the advantages provided by a small number of ancillas. For the case that a k-qubit ancilla (k≤n) is available, we obtain a sample complexity lower bound of Ω(2 (n-k)/3 ) for any nonconcatenating protocol, and a stronger lower bound of Ω(n 2n-k ) for any nonadaptive, nonconcatenating protocol, which is shown to be tight. We also show how to apply the ancilla-assisted estimation protocol to a practical quantum benchmarking task in a noise-resilient and sample-efficient manner, given reasonable noise assumptions. Our results provide a practically interesting example for quantum advantages in learning and also bring insights for quantum benchmarking.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

A Computational Framework to design 3D stiffness gradient acoustic metamaterials for impedance matching

Acoustic waves play a crucial role in various applications, including medical imaging, non-destructive testing, and sonar systems. One of the significant challenges in these applications is impedance matching, which is essential for minimizing reflections and maximizing the transfer of acoustic energy between different media. Acoustic metamaterials offer a promising solution to this challenge. In addition to impedance control, gradient stiffness can enhance structural efficiency and enable spatial control of wave propagation, making it a valuable feature in acoustic metamaterial design. In this pa- per, we present our developed computational method to design 3D stiffness gradient acoustic metamaterials for impedance matching. The key steps in our approach include generating initial designs using a periodic covariance function to provide unit cells that are both periodic on the boundaries and randomly formed inside the unit cell. Furthermore, we integrated manufacturing constraints into the design process, ensuring that the structures are interconnected for fabrication. We propose two computational optimization algorithms: GenUnit, based on a non-dominated sorting genetic algorithm (NSGA-II), and MLMatch, which leverages differentiable machine learning. The two approaches are not separate contributions but complementary com- ponents of a unified framework. GenUnit requires no training data and directly interfaces with physics-based simulations, making it highly accurate but slower for large-scale exploration. In contrast, MLMatch is data-hungry during training but, once trained, enables near-instantaneous inference and broad design-space coverage. Together, they form a hybrid strategy: ML- Match rapidly explores the global design space, and GenUnit provides local refinement with high-fidelity accuracy. This balance between training cost, inference time, and precision is the motivation for including both methods in the same study. We applied this dual-algorithm framework to generate two metallic-based metamaterial designs that match the acoustic impedance of water while exhibiting a controlled gradient in stiffness (from stiff to soft). The stiffness gradient is particularly advantageous in applications where one side of the structure must interface with soft or sensitive surfaces, such as human tissue or delicate components. Here, this work paves the way for improved materials in various acoustic applications, particularly in ultrasound devices, by providing better impedance.

Metamaterial↗

Adaptive methods of generating complex light arrays

Structured light arrays of various shapes have been a cornerstone in optical science, driven by the complexities of precise and adaptable generation. This study introduces an approach using a spatial light modulator (SLM) as a generator for these arrays. By projecting a holographic mask onto the SLM, it functions simultaneously as an optical convolution device, focusing mechanism, and structured light beam mask. Our approach offers unmatched versatility, allowing for the experimental fabrication of traditional beam arrays like azimuthal Laguerre–Gaussian (LG), Bessel–Gaussian (BG), and Hermite–Gauss (HG) in the far-field. Notably, it has enabled a method of generating Ince–Gauss (IG) and LG radial mode beam arrays using a convolution solution. Our system provides exceptional control over array periodicity and intensity distribution, bypassing the Talbot self-imaging phenomenon seen in traditional setups. We provide an in-depth theoretical discussion, supported by empirical evidence, of our far-field results. This method has vast potential for applications in optical communication, data processing, and multi-particle manipulation. It paves the way for rapid generation of structured light with high spatial frequencies and complex shapes, promising transformative advances in these domains.

Optics↗

Intra-Molecular Isotope Study of Light Hydrocarbons

Light hydrocarbons (C 1 -C 10 ) are the largest fraction of petroleum hydrocarbons and some of the most ubiquitous and mobile fluids within sedimentary basins. It has been increasingly recognized that hydrocarbons of varying chain-lengths can be stable even under mantle conditions and that their fluxes may play a key role in the carbon dynamics of the Earth. Major formation mechanisms of these light hydrocarbons include microbial, thermogenic, and abiogenic origins. Despite their proven utility, conventional approaches using the bulk or global stable isotopes of light hydrocarbons are often not sufficient to distinguish their sources (particularly, biogenic vs. abiogenic), maturation stages/temperatures, and migration-degradation processes. Most natural compounds, including light hydrocarbons, are composed of a set of diverse isotopic molecules that differ in the number of isotopic substitutions and/or positions of isotopic substitution within a given molecules. Many of light hydrocarbon molecules contain hydrogen and carbon in energetically non-equivalent positions: isotopomers or position-specific (intra-molecular) isotope fractionation. Position-specific isotopic compositions can differ due either to equilibrium or to path-dependent kinetic or biological processes. Thus, the position-specific isotopic fractionation between different carbon and hydrogen positions within a single molecular compound could be used regardless of their reactants and other products. We hypothesize that the formation, transport and degradation processes of light hydrocarbons in the subsurface induce and control significant, perhaps unique position-specific 13 C/ 12 C and 2 H/ 1 H isotope fractionation. In this proposal, we propose to develop a new dimension in stable isotope geochemistry of light hydrocarbons: intra-molecular isotope study of light hydrocarbons. The specific objectives of our proposal include: (a) develop robust and routine quantitative nuclear magnetic resonance (NMR) methods for high-precision/high-accuracy isotopomer analysis of propane and other light hydrocarbons (C 3 -C 10 ), (b) gain a first clear picture on position-specific δ 2 H and δ 13 C values of select light hydrocarbons of both natural and industrial sources, including samples of natural gases (C 3 and possibly C 4 -C 5 ) collected from select sedimentary basins with conventional and unconventional reservoirs, (c) acquire information on position-specific 13 C/ 12 C and 2 H/ 1 H isotope fractionation of light hydrocarbons in key natural processes (thermogenic formation and oxidative degradation) based on well-controlled laboratory experiments, and (d) establish a general framework for interpreting/modeling position-specific 13 C/ 12 C and 2 H/ 1 H isotope compositions of light hydrocarbons. Intra-molecular isotope study of light hydrocarbons is expected to open up great potentials that the bulk and position-specific isotope fractionation of light hydrocarbons, in combination with mathematical/theoretical kinetic models, could provide unprecedented wealth of information on the sources, transport, and sinks of light hydrocarbons in sedimentary basins and deep Earth.

03 NATURAL GAS↗

PROSPECT-II physics opportunities

We report the precision reactor oscillation and spectrum experiment, PROSPECT, has made world-leading measurements of reactor antineutrinos at short baselines. In its first phase, conducted at the high flux isotope reactor (HFIR) at Oak Ridge National Laboratory, PROSPECT produced some of the strongest limits on eV-scale sterile neutrinos, made a precision measurement of the reactor antineutrino spectrum from 235 U, and demonstrated the observation of reactor antineutrinos in an aboveground detector with good energy resolution and well-controlled backgrounds. The PROSPECT collaboration is now preparing an upgraded detector, PROSPECT-II, to probe yet unexplored parameter space for sterile neutrinos and contribute to a full resolution of the reactor antineutrino anomaly, a longstanding puzzle in neutrino physics. By pressing forward on the world’s most precise measurement of the 235 U antineutrino spectrum and measuring the absolute flux of antineutrinos from 235 U, PROSPECT-II will sharpen a tool with potential value for basic neutrino science, nuclear data validation, and nuclear security applications. Following a two-year deployment at HFIR, an additional PROSPECT-II deployment at a low enriched uranium reactor could make complementary measurements of the neutrino yield from other fission isotopes. PROSPECT-II provides a unique opportunity to continue the study of reactor antineutrinos at short baselines, taking advantage of demonstrated elements of the original PROSPECT design and close access to a highly enriched uranium reactor core.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Preparation of a uranium monocarbide anode and electrochemical characterization in molten LiCl-KCl-UCl 3

Porous uranium carbide (UC) pellets possessing moderate electrical conductivity were synthesized by reaction of UO 2 with graphite at temperatures up to 1550°C under rough vacuum. Conversions as high as 98% were achieved at soak times of 2-4 hours. The electrochemistry of the UC pellets in molten LiCl-KCl-6.5 wt% UCl 3 was explored using a variety of techniques including DC polarization methods, cyclic voltammetry, chronopotentiometry and bulk electrolysis. Here, the electrode reaction for anodic dissolution was found to be kinetically controlled by dissociation of UC to a transition state complex that was hypothesized to consist of a uranium atom partially complexed by chloride ions. Precise measurements of current efficiencies using chronopotentiometry indicated upper limits of 90.9 ± 3.4% and 98.3 +1.7/-3.7% for anode and cathode, respectively, when operating at anodic overpotentials near +300 mV. Bulk electrolysis of a UC pellet performed by passing 98% of the theoretical charge resulted in nearly complete recovery of its uranium content as highly pure metal at the cathode.

36 MATERIALS SCIENCE↗