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At least 271 records · Page 15

Heterogeneous hydroformylation of alkenes by Rh-based catalysts

Heterogeneously catalyzed hydroformylation reactions avert the problems of separation in homogeneous reactions, reduce the discharge of phosphorus-containing wastes, and prevent the loss of precious metals. This review summarizes the developments of catalysts for heterogeneous hydroformylation in the last decade and proposes potential modification methods for future improvements. The hydroformylation properties of different reactants are compared in order to emphasize the fact that various olefins face unique challenges. The hydroformylation of ethylene requires the enhancement of catalytic activity and chemoselectivity, whereas that of propylene needs improvements in both chemoselectivity and regioselectivity. The hydroformylation of longer-chain olefins and styrene seeks further improvement in regioselectivity. The catalytic properties of activity, selectivity, and stability can be tuned through electronic effects (bimetallic effects, phosphine ligands, and single-atom catalysts), steric hindrance (encapsulation structures, diphosphine ligands, and local functional groups), and reaction condition optimization (temperature, pressure, and solvents). Furthermore, the understanding of these effects is critical in future catalyst design for heterogeneous hydroformylation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Revolutionizing observations and predictability of Arctic system dynamics through next-generation dense, heterogeneous and intelligent wireless sensor networks with embedded AI

The Arctic region is a complex and dynamic system, where changes in temperature and partitioning between water in solid, liquid and vapor phase are fundamentally reshaping hydro-biogeochemical fluxes from the bedrock to the atmosphere. The increasing temperature and frequency of extreme heat, precipitation and fire events (Wang et al., 2017; Meredith et al., 2019) have critical consequences for the Arctic ecosystems and people, as well as for the global climate system. Although many observational and remote sensing activities have been on-going, detailed ecosystem processes – particularly related to controls on and impacts of permafrost thaw – are difficult to detect or measure. To improve the understanding and prediction of these extreme events and their consequences, we need a revolution in the way we collect ground-based observations from hillslope to pan-Arctic scales and couple them with satellite imagery and models to deliver rich, actionable, and scale-appropriate data.

54 ENVIRONMENTAL SCIENCES↗

Tussock tundra surface temperatures, ambient air and incoming photosynthetically active radiation measured at the NGEE Arctic Council site, 2021 - 2023

This dataset contains temperature measurements carried out along two fiber optics cables/lines (150 m each) laid out along the ground at the Next Generation Ecosystem Experiment (NGEE) Arctic site near Council, Alaska. The lines traverse an heterogeneous part of the tussock tundra site including thermokarst features and lichen dominated sections of the tundra. Measurements were done using a Sensornet Oryx DTS, a Distributed Temperature sensor that was installed in September 2021 and taken down in August 2023. The sensor was powered by solar power with data being collected every 30 minutes at 1 m resolution. In addition to these measurements air temperature and incoming photosynthetically active radiation (PAR) are provided. These measurements are co-located with the NGEE Arctic Council eddy flux and meteorological station (AmeriFlux ID US-NGC). Included are six *.csv files (four data files and two reporting format files) and two *.kml files. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

Air temperature↗

CHELAX-BNF: Fast Response Temperature by airborne measurements

The original data were collected on board the ARM Aerial Facility ArcticShark uncrewed aerial system (UAS; https://www.arm.gov/capabilities/observatories/aaf/uas ) during the “Characterizing HEterogeneous Land-Atmosphere eXchanges at BNF” field campaign (CHEAX-BNF; https://arm.gov/research/campaigns/aaf2025CHELAX-BNF ). The ARM Aerial Facility ArcticShark UAS was based at the public-use airport of Posey Field, AL (FAA LID: 1M4, 34.28027778° N, 87.60055556° W, 283m MSL) from May 28 to June 23, 2025. The ArcticShark UAS performed 5 flights, including 4 research flights over the BNF Main Site (ARM Mobile Facility 3, https://arm.gov/capabilities/observatories/amf ) and Supplemental Facilities to measure atmospheric state, turbulence, surface IR temperature and imagery, aerosol number concentration, and aerosol size distribution. The current data set presents fast response temperature in the atmospheric boundary layer and lower free troposphere measured on the airborne platform throughout the field campaign. The primary instruments used to create the current data set were the fine wire thermocouple probe, the Aircraft Integrated Meteorological Measurement System (AIMMS-30), the Pitot-static system (part of UAS flight control), and the infrared gas analyzer sensor for H2O and CO2 (LI-840). All parameters used in temperature calculations (static pressure, True Air Speed, and absolute humidity in the form of dew point temperature) were included in the data set. For user convenience, one additional parameter was also included: the type of flight flag (level, up, down, turn, and combination of thereof).

Air temperature, fast response↗

Elevated temperature ductility dip in an additively manufactured Al-Cu-Ce alloy

The deformation and failure mechanisms of Al-9Cu-6Ce (wt%) based alloys fabricated with laser powder bed fusion were investigated from room temperature to 400°C. The yield and ultimate tensile strengths decreased monotonically with increase in temperature, but the tensile elongation dipped unexpectedly at elevated temperatures and exhibited a minimum at 300°C. The dip in tensile elongation occurred with a concomitant dip in strain-rate sensitivity (SRS) of deformation. The as-fabricated alloy microstructure was heterogeneous, and the heat affected zone (HAZ) underneath the melt pool boundary was prone to strain localization. At 300 °C, the reduced SRS promoted the progression of strain localization in the HAZ leading to failure initiation and the dip in tensile elongation. Furthermore, a higher SRS or strain-hardening rate at other temperatures improved the tensile elongation by slowing the progression of strain localization in the HAZ such that failure initiated by other mechanisms elsewhere in the microstructure. Notably, the tensile elongation was limited by the defect structure only in a narrow temperature range (150 - 200 °C) while at other temperatures it was limited by the inherent microstructural features. This investigation exemplifies unexpected deformation and failure mechanisms possible in heterogeneous microstructures that result from additive manufacturing.

36 MATERIALS SCIENCE↗

Effect of heterogeneous microstructure on the tensile and creep performances of cast Haynes 282 alloy

Precipitation-strengthened Ni-based superalloys are leading candidate materials for advanced ultra-supercritical (A-USC) plants with steam conditions up to 760 °C (1400 °F) and 35 MPa (5 ksi). This study evaluates representative specimens from a large casting of Haynes 282 to study the effect of microstructural heterogeneity on the mechanical behavior of this alloy. The tensile test results of cast Haynes 282 over the temperature range 20–816 °C exhibited lower tensile strength and ductility in comparison with the reference wrought Haynes 282. However, the creep rupture tests of the cast alloy below 704–788 °C and 190–431 MPa presented a similar stress-Larson-Miller parameter to that of the wrought material. Microstructural and dislocation characterizations using scanning electron microscopy, conventional transmission electron microscopy, and scanning transmission electron microscopy in conjunction with energy dispersive X-ray spectroscopy were performed to understand the microstructural evolution before and after the mechanical tests. The heterogeneous microstructures of the cast Haynes 282 material, including the coarse grains, potential casting defects, and a bimodal size distribution of γ' precipitates, were detrimental to the tensile behavior, whereas the coarse-scale grains had a positive effect on the creep performance because diffusional creep was the dominant creep mechanism.

tensile testing↗

Kinetics of Magnetic Skyrmion Crystal Formation from the Conical Phase

The particle-like magnetic skyrmion or skyrmion lattice (SkX) formation has promoted strong application and fundamental science interests. Despite extensive research, the kinetic of the SkX development is much less understood because of the ultrafast spin rotation and high sensitivity to external perturbations. In this work, using in situ Lorentz transmission electron microscopy, we successfully measured the dynamics of SkX formation from the conical phase with precise control of both the temperature and the magnetic field. We discovered that the Avrami equation can accurately describe the transition process with an initial Avrami constant around 1, suggesting that the rate-limiting step for the quasiparticle lattice formation is one-dimensional heterogeneous nucleation of individual skyrmions. A modified Arrhenius rate law is established, with an energy barrier that has a square-root dependence on temperature and a quadratic dependence on the magnetic field. This study paves the way toward precise and predictable manipulation of topological spin structures.

36 MATERIALS SCIENCE↗

Computational discovery of ultra-strong, stable, and lightweight refractory multi-principal element alloys. Part I: design principles and rapid down-selection

Abstract Refractory metal-based multi-principal element alloys (MPEAs) are compelling materials for high-temperature (1000–2000 K) structural applications. However, only a minuscule fraction of their vast and heterogeneous compositional design space has been explored, leaving many potentially interesting alloys undiscovered. In this two-part work, a large region of the 11-element Al-Cr-Fe-Hf-Mo-Nb-Ta-Ti-V-W-Zr design space is computationally explored to identify refractory MPEAs with simultaneously high yield strength or specific yield strength and body-centered cubic (BCC) solid solution stability. In Part I , two case studies illuminate key factors and considerations in the yield strength versus phase stability tradeoff, provide guidelines for narrowing the expansive design space, and identify many candidates predicted to be stronger than refractory MPEAs reported to date, with BCC phase stability. Our findings indicate that medium entropy ternary alloys can outperform alloys with more elements and highlight the importance of exploring regions away from the equiatomic center of composition space.

36 MATERIALS SCIENCE↗

Echogenic Segmentation for Ultrasonic Measurements of Spatially Distributed Properties in Solids

An ultrasonic (US) pulse propagating between transducer-receiver responds cumulatively to distributed material properties it encounters, such as temperature distribution. Such convolution makes the unique reconstitution of distributions impossible short of applying tomographic techniques. However, spatial heterogeneity in material properties is readily revealed by segmenting the US propagation path with echogenic features (EF), producing a train of echoes delayed as a function of segmentally localized properties. Unfortunately, in low attenuating waveguides (WGs), primary and trailing echoes (TE) interfere, limiting the number, density, and placement of EFs we can use. We report the design guidelines for creating US-segmented WGs for measuring distributed properties, in which the impact of TEs is minimized or eliminated. Two waveguide designs using these principles have been tested in spatially distributed temperature measurements in high-temperature or restrictive environments.

Walton, Kenneth↗

Influence of Soil Moisture on the Development of Organized Convective Systems in South America

Abstract This study investigates the role of soil moisture (SM) on the initiation and organization of convective systems using the convection‐permitting ICOsahedral Non‐hydrostatic (ICON) model. We conduct two sets of experiments: a Control experiment with interactive SM and a fixed SM experiment (FixedSM) with invariable SM conditions. We focus on two regions in South America: the Amazon and southeastern South America (SESA). Larger organized convective systems are associated with greater SM heterogeneity in both regions, though other large‐scale synoptic influences affect the robustness of this relationship in SESA. These results remain largely unaffected by disabling the effects of precipitation on SM in the FixedSM experiment, and complementary analyses using satellite‐based estimates of SM and precipitation support these findings. Spatial compositing of mesoscale environments in the Amazon shows the presence of well‐defined SM gradients, at a length scale of a few hundred kilometers, many hours before convective system detection. Larger SM gradients correspond to larger gradients in thermodynamic variables, particularly surface temperature and sensible heat flux, and are associated with larger convective systems. Overall, our findings suggest that surface heterogeneities such as SM gradients not only affect deep convection initiation, as previously suggested, but they can also encourage the growth and organization of convective systems into larger clusters, particularly in the absence of significant synoptic influences.

54 ENVIRONMENTAL SCIENCES↗

Dynamic Nanoscale Spatial Heterogeneity in a Perovskite-to-Brownmillerite Topotactic Phase Transformation

Phase transitions are omnipresent in modern condensed matter physics and its applications. In solids, first-order phase transformations typically occur by nucleation and growth under nonequilibrium conditions. Under constant external conditions, e.g., constant annealing temperature and pressure, the nucleation and growth dynamics are often thought of as spatially and temporally independent. Here, in situ Bragg X-ray photon correlation spectroscopy (XPCS) reveals nanoscale spatial and dynamical heterogeneity in the perovskite-to-brownmillerite topotactic phase transformation in La 0.7 Sr 0.3 CoO 3 thin films annealed under constant reducing conditions over a time span of multiple hours. Specifically, a time scale associated with domain growth remains stable, with a corresponding domain wall speed of v d = 6 ± 0.5 × 10 –4 nm/s (2 ± 0.2 nm/h), while a slower time scale, associated with temperature-driven depinning of domains, leads to accelerating dynamics with time scales following an aging power law with exponent −2.2 ± 0.5. This experiment demonstrates that Bragg XPCS is a powerful tool to study nanoscale dynamics in structural phase transformations, with the ability to extract quantitative average values related to nanodomain motion in situ. Furthermore, the results are relevant for phase engineering of phase-change devices, as they show that nanoscale dynamics, linked to domain and domain-wall motion, can continuously evolve and speed up with time, even hours after the initiation of the phase transformation, with potential repercussions on electrical performance.

X-ray photon correlation spectroscopy↗

Temperature-Dependent Communication between Pt/Al 2 O 3 Catalysts and Anatase TiO 2 Dilutant: the Effects of Metal Migration and Carbon Transfer on the Reverse Water–Gas Shift Reaction

In heterogeneous catalysis, unexpected effects from the supposedly inert reactor dilutant are not rare, but related understanding is lacking and inconsistent. Here we report investigations of the impacts of the anatase TiO 2 dilutant on the reverse water-gas shift (rWGS) reaction over Pt/Al 2 O 3 catalysts. Combining detailed kinetic data with microscopic and spectroscopic results, we demonstrate that the catalyst-dilutant communication depends on temperature. At high temperature (400 °C), Pt migrate from Al 2 O 3 to TiO 2 , resulting in higher dispersion and activity, without changing reaction mechanisms. The Pt migration is general to catalysts of different Pt nuclearity and various oxide dilutants. In contrast, at low temperature (250 °C), carboxylic acids (in particular acetic acid) present in the ambient air and adsorbed on TiO 2 are transferred onto Al 2 O 3 in close contact, effectively blocking the formate rWGS pathway. As a result, the rWGS can only proceed through the carboxyl pathway, and hence is significantly slower. The acetate transfer affects catalysts of different Pt nuclearity and support, but is unique to anatase TiO 2 dilutant. As the acetate layer is slowly removed under H 2 or the rWGS stream, the activity recovers. This work elucidates the complicated communication between catalysts and dilutants, which has general implications in heterogeneous catalysis, and resolves inconsistency in related reports in the literature. Finally, the impacts that anatase TiO 2 dilution has on the rWGS also unveil mechanistic understanding that further confirms the two co-existing rWGS pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interactive effects of precipitation, temperature, and grazing pressure on the net ecosystem carbon balance of grazing lands across the continental United States

Grazing lands cover approximately one-third of the contiguous United States, support much of the nation's beef production, and are an important component of the U.S. terrestrial carbon budget. In this study, we quantified net ecosystem carbon balance (NECB), the net status of grazing lands as a carbon sink (C-sink) or source (C-source) and a key determinant of soil health and productivity. Our primary objective was to synthesize multiple years of annual NECB across heterogeneous grazing lands across the continental U.S and evaluate annual NECB against physical drivers (mean annual precipitation (MAP), mean annual temperature (MAT), vegetation, and moisture condition) and management practices (grazing pressure index (GPI) and fertilization history). We hypothesized that (1) NECB is higher in mesic and fertilized grasslands; (2) NECB increases with MAP and MAT but decreases with GPI; and (3) interactive effects exist among MAP, MAT, and GPI. Using carbon fluxes measured by eddy covariance towers and methane emissions including both enteric methane and manure derived from stocking rates across seven USDA Long-term Agroecosystem Research Network sites, we found: (1) grazing lands were a C-sink or carbon neutral at most sites; (2) vegetation type, moisture conditions, or fertilization had no significant effect on NECB; (3) NECB increased with MAP and MAT, but decreased with a higher GPI; and (4) MAT had a significant positive effect on NECB when MAP exceeded 750 mm (greater water availability). The effect of GPI on NECB was significantly negative when MAP was below 1000 mm, significantly negative when MAT < 12 °C and significantly positive when MAT > 16 °C. Thus, most grazing lands in our study acted as C-sinks unless water deficit, low temperature, or heavy grazing were interactively present. Understanding how climate and management influence NECB of grazing lands is key to maintaining resilient agroecosystems that secure beef production and sustain rural prosperity.

LTAR↗

Heterogeneous Fe-N-C Catalyst for Aerobic Dehydrogenation of Hydrazones to Diazo Compounds Used for Carbene Transfer

Organic diazo compounds are versatile reagents in chemical synthesis and would benefit from improved synthetic accessibility, especially for larger scale applications. Here, we report a mild method for the synthesis of diazo compounds from hydrazones using a heterogeneous Fe-N-C catalyst, which has Fe ions dispersed within a graphitic nitrogen-doped carbon support. The reactions proceed readily at room temperature using O 2 (1 atm) as the oxidant. Aryl diazoesters, ketones, and amides are accessible, in addition to less stable diaryl diazo compounds. Initial-rate data show that the Fe-N-C catalyst achieves faster rates than a heterogeneous Pt/C catalyst. The oxidative dehydrogenation of hydrazones may be performed in tandem with Rh-catalyzed enantioselective C–H insertion and cyclopropanation of alkenes, without requiring isolation of the diazo intermediate. Furthermore, this sequence is showcased by using a flow reactor for continuous synthesis of diazo compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In situ high-temperature X-ray diffraction study of Sc-doped titanium oxide nanocrystallites

Titanium dioxide is an inexpensive wide-gap highly ionic semiconductor with striking photocatalytic capabilities in several heterogeneous photoredox reactions. A small crystal size is desirable to maximize the surface area, since photocatalytic reactions occur at the surface of a photocatalyst. Presented in this work are the synthesis and microstructural characterization of 4 at.% Sc-doped TiO 2 (4SDT) prepared by water-based co-precipitation. The crystal structure of 4SDT was examined via in situ high-temperature powder X-ray diffraction experiments from 25 to 1200°C. Rietveld analysis revealed single-phase anatase up to 875°C, while at 900°C the anatase-to-rutile phase transformation occurred and at higher temperatures additional reflections of Sc-rich phases (Sc 2 TiO 5 from 975°C and Ti 3 Sc 4 O 12 or Sc 2 O 3 at 1200°C) were observed. Debye function analysis (DFA) was applied to model the total scattering pattern directly in reciprocal space, allowing the reconstruction of Ti vacancies. Both Rietveld and DFA methods were applied to estimate the nanocrystallite size and shape with consistent growth in crystallite size with temperature: an ellipsoid shape with equatorial ~4.7 nm / axial (001) ~6.9 nm at 25°C to equatorial ~27.9 nm / axial (001) ~39.6 nm at 900°C refined by Rietveld analysis, versus a cylinder shape with D a , b = 4.3 nm and size dispersion σ ab = 1.5 nm, L c = 4.9 nm and σ c = 2.3 nm at 25°C to D a , b = 21.4 nm, σ ab = 8.3 nm, L c = 23.9 and σ c = 10.9 nm at 900°C estimated by DFA. The microstructural changes obtained by Rietveld and DFA methods were supported by high-resolution transmission electron microscopy image analysis, as well as by the less direct nitrogen sorption techniques that provide information on the size of non-agglomerated and dense particles. The Ti site-occupancy factor showed a linear increase from 0.6–0.8 at 25°C to unity at 900°C for anatase, and from ~0.7 at 900°C to unity at 1200°C for rutile, via Rietveld analysis and DFA.

36 MATERIALS SCIENCE↗

Extended continuous cooling transformation diagram for 410 stainless steel encompassing δ → γ and γ → αʹ transformations determined by dilatometry

In this study, we use dilatometry to construct an extended Continuous Cooling Transformation (CCT) diagram for 410 stainless steel, capturing both δ → γ and γ → αʹ transformations specifically for directed energy deposition (DED) additive manufacturing (AM) applications. To ensure that the findings are representative of AM specific microstructures and compositions, dilatometry coupons were extracted from a wire arc DED wall, thereby preserving the inherent microstructural and compositional variability within the material. The on-heating phase transformations, including A c1 , A c3 , and γ → δ, were found to be essentially location independent, despite the typical heterogeneity associated with AM. Conversely, increasing cooling rates were observed to shift the start and finish temperatures of both δ → γ and γ → αʹ transformations to lower values. The resulting extended CCT diagram offers a more complete depiction of phase transformation behavior in the system, enabling accurate microstructure evolution modeling and residual stress predictions specifically for directed energy deposition additive manufacturing applications.

Additive manufacturing↗

The role of cool-flame fluctuations in high-pressure spray flames, studied using high-speed optical diagnostics and Large-Eddy Simulations

Here this work investigates the low- and high-temperature ignition and combustion processes, applied to the Engine Combustion Network Spray A flame, combining advanced optical diagnostics and large-eddy simulations (LES). Simultaneous high-speed (50 kHz) formaldehyde (CH 2 0) planar laser-induced fluorescence (PLIF) and line-of-sight OH* chemiluminescence imaging were used to measure the low- and high-temperature flame, during ignition as well as during quasi-steady combustion. While tracking the cool flame at the laser sheet plane, the present experimental setup allows detection of distinct ignition spots and dynamic fluctuations of the lift-off length over time, which overcomes limitations for flame tracking when using schlieren imaging. After significant development to improve LES prediction of the low-and high-temperature flame position, both during the ignition processes and quasi-steady combustion, the simulations were analyzed to gain understanding of the mixture variance and how this variance affects formation/consumption of CH 2 0. Analysis of the high-temperature ignition period shows that a key improvement in the LES is the ability to predict heterogeneous ignition sites, not only in the head of the jet, but in shear layers at the jet edge close to the position where flame lift-off eventually stabilizes. The LES analysis also shows concentrated pockets of CH 2 0, in the center of jet and at 20 mm downstream of the injector (in regions where the equivalence ratio is greater than 6), that are of similar length scale and frequency as the experiment (approximately 5–6 kHz). The periodic oscillation of CH 2 0 match the frequency of pressure waves generated during auto-ignition and reflected within the constant-volume vessel throughout injection. The ability of LES to capture the periodic appearance and destruction of CH 2 0 is particularly important because these structures travel downstream and become rich premixed flames that affect soot production.

42 ENGINEERING↗

CO 2 –Brine Contact Angle Measurements on Navajo, Nugget, Bentheimer, Bandera Brown, Berea, and Mt. Simon Sandstones

In this study, contact angles were measured for CO 2 bubbles on six different sandstones (Navajo, Nugget, Bentheimer, Bandera Brown, Berea, and Mt. Simon) that could potentially represent properties of CO 2 storage depositional environments. The impacts of pressure and temperature were studied by focusing on the CO 2 phase behavior in three different scenarios: gaseous, liquid, and supercritical conditions. Despite controlling the sample preparation and cleanliness, CO 2 -brine equilibration conditions, and pressure and temperature, there were inconsistencies in contact angle trends that could largely be attributed to natural sample heterogeneity resulting from localized variations in topography, surface roughness, and mineral composition across the surface. Despite these variations, the analysis of 298 measurements from this study showed that 81% of the contact angles were below 40° representing strongly water-wet to (moderately) water-wet behaviors. Also, 17.3% of the measurements were between 40° and 60° (weakly water-wet) and primarily belonged to small CO 2 bubbles (< 500 μm) that were heavily impacted by localized surface heterogeneity in natural sandstone samples. Additionally, only 1.7% of the measurements had angles greater than 60° and could be classified as CO 2 -wet behavior, but these measurements occurred on extremely small bubbles (100-200 μm) that were very dependent on localized surface heterogeneity. While some of the detailed physics of the CO 2 -brine-sandstone interface is still poorly understood, from an application standpoint, the sandstones of this study were best characterized as strongly water-wet to (moderately) water-wet.

03 NATURAL GAS↗