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At least 235 records · Page 13

Catalytic Deconstruction of Ethylene Vinyl Acetate Copolymer and Polyethylene Mixtures via Hydroconversion: Challenges and Solutions

We explore hydrogenolysis over ruthenium supported on zirconia (Ru/ZrO 2 ) and hydrocracking over platinum (Pt) supported on zeolites as an effective end-of-life strategy for ethylene vinyl acetate (EVA)–a widely used performance heat sealant in hard-to-recycle multilayer packaging. For Ru/ZrO 2 hydrogenolysis, EVA reacts slower than low-density polyethylene (LDPE) and the catalyst deactivates due to carbonaceous deposits originating from polyenes generated in situ during EVA thermal degradation. High H 2 pressures and temperatures can overcome catalyst deactivation; however, CH 4 yields are excessive due to cascade hydrogenolysis stemming from strong C=C/metal interactions. Polyene hydrogenation allows chains anchored by C=C to desorb from Ru, shifting product selectivity from CH 4 to higher-value liquids. Hydrogenolysis of mixed EVA and linear low-density polyethylene (LLDPE), mirroring typical frozen food packaging formulations, results in comparable catalyst activity and CH 4 yield as the pure EVA resin. For Pt/zeolite hydrocracking, pure EVA and EVA:LLDPE mixtures are deconstructed to propane or light naphtha with minimal CH 4 production. Among catalysts tested, Pt/HY gives the highest liquid productivity (g C5+products /g cat ·h). Furthermore, these findings showcase the recalcitrant nature of EVA and its associated mixtures for Ru/ZrO 2 hydrogenolysis, highlighting that hydrocracking catalysts may be superior for complex packaging waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Techno-economic and life cycle analysis of synthetic natural gas production from low-carbon H 2 and point-source or atmospheric CO 2 in the United States

Synthetic natural gas (SNG) is of great interest in reducing fossil energy consumption while maintaining compatibility with existing NG infrastructure and end-use applications equipment. SNG can be produced using clean H 2 generated from renewable or nuclear energy and CO 2 captured from stationary sources or the atmosphere. In this study, we develop an engineering process model of SNG production using Aspen Plus® and production scales reported by the industry. We examine the levelized cost and life cycle greenhouse gas (GHG) emissions of SNG production under various CO 2 supply scenarios. Considering the higher cost of H 2 transportation compared with CO 2 transportation, we assume that CO 2 feedstock is transported via pipeline to the H 2 production location, which is collocated with the SNG plant. We also evaluate the cost of CO 2 captured from the atmosphere, assuming the direct air capture process can occur near the SNG facility. Depending on the CO 2 supply chain, the levelized cost of SNG is estimated to be in the range of $\$45–76$ per million British thermal units (MMBtu) on a higher heating value (HHV) basis. The SNG production cost may be reduced to $\$27–57$/MMBtu-HHV by applying a tax credit available in the United States for low-carbon H 2 production (45V). With a lower electricity price of 3¢/kWh for water electrolysis and accounting for a 45V tax credit, the SNG cost reaches parity with the cost of fossil NG. Depending on the CO 2 supply chain, SNG can reduce life cycle GHG emissions by 52–88% compared with fossil NG.

03 NATURAL GAS↗

Long-slit spectral study of the unusual post-interacting galaxy Arp 263

ABSTRACT Arp 263 is a single irregularly shaped galaxy with intense star formation. Its short tidal features of low brightness visible in both optics and the H i line, as well as the strong non-circular motion of atomic gas in the outskirts, give pieces of evidence of a recent merging with some intruder, non-observed directly. We carried out spectral observations of this galaxy at the 6 m telescope of the Special Astrophysical Observatory. The spectra for three positions of the spectral slit were obtained: two of them cross the central region of the galaxy and the third one runs along the nearly straight narrow chain of clumps of emission gas with a length of 4–5 kpc. We derived the profiles of velocity, fluxes, and oxygen abundances (O/H) along the slits. We confirm that within the radius of several kpc the galaxy rotates regularly. The maximal value of the rotational velocity allows us to conclude that the dark mass of the galaxy prevails over the mass of its visible components. The observed velocity profile along the peripheral star-forming chain gives pieces of evidence that it is located outside of the plane of the disc, and the gas that formed the chain is probably falling back on to the disc after being ejected from the galaxy. We discuss that the observed chain of clumps is the result of gravitational instability of the gaseous filament.

Astronomy & Astrophysics↗

First estimation of high-resolution solar photovoltaic resource maps over China with Fengyun-4A satellite and machine learning

Fengyun-4A (FY-4A), which is the latest-generation Chinese geostationary meteorological satellite, measures solar reflection and thermal emission with high temporal, spatial, and spectral resolutions. It is expected to be highly beneficial for solar resource assessment and forecasting in China. This study is the first to estimate, using FY-4A and a random forest model, the global horizontal irradiance (GHI) at a 4-km–15-min spatio-temporal resolution over China, as a means to arrive at a solar photovoltaic (PV) resource map. In terms of GHI estimates, the root mean square error and mean bias error between hourly measured and retrieved values are 147.02 (35.2%), –5.64 W/m 2 (–1.4%), respectively, whereas the values of daily estimates are 29.20 (18.0%), –2.97 W/m 2 (–1.3%). The retrieval accuracy is found much better for instances with solar zenith angles smaller than 60°. Relatively larger errors are found at locations in the Sichuan Basin and northeastern China, which can be attributed to bright surfaces and/or strong cloud transients. With the retrieved irradiance, PV resource is derived through a physical model chain. The annual mean PV resource map suggests that, over most of the west areas, the annual mean effective irradiance exceeds 1700 kWh/m 2 , with the highest value found in Tibet (around 2000 kWh/m 2 per annum). Eastern China has an annual effective irradiance of only 1300–1500 kWh/m 2 . In conclusion, the region with poorest solar resource is the Sichuan Basin (less than 1100 kWh/m 2 per annum).

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Light‐driven Transformation of Carbon Monoxide into Hydrocarbons using CdS@ZnS : VFe Protein Biohybrids

Enzymatic Fisher-Tropsch (FT) process catalyzed by vanadium (V)-nitrogenase can convert carbon monoxide (CO) to longer-chain hydrocarbons (>C2) under ambient conditions, although this process requires high-cost reducing agent(s) and/or the ATP-dependent reductase as electron and energy sources. Using visible light-activated CdS@ZnS (CZS) core-shell quantum dots (QDs) as alternative reducing equivalent for the catalytic component (VFe protein) of V-nitrogenase, we first report a CZS : VFe biohybrid system that enables effective photo-enzymatic C−C coupling reactions, hydrogenating CO into hydrocarbon fuels (up to C4) that can be hardly achieved with conventional inorganic photocatalysts. Surface ligand engineering optimizes molecular and opto-electronic coupling between QDs and the VFe protein, realizing high efficiency (internal quantum yield >56 %), ATP-independent, photon-to-fuel production, achieving an electron turnover number of >900, that is 72 % compared to the natural ATP-coupled transformation of CO into hydrocarbons by V-nitrogenase. The selectivity of products can be controlled by irradiation conditions, with higher photon flux favoring (longer-chain) hydrocarbon generation. The CZS : VFe biohybrids not only can find applications in industrial CO removal for high-value-added chemical production by using the cheap, renewable solar energy, but also will inspire related research interests in understanding the molecular and electronic processes in photo-biocatalytic systems.

Chemistry↗

Alloy selective optical sorting of mixed post-consumer aluminum scrap streams

Shredded post-consumer non-ferrous scrap stream, also known as Zorba, contains a mixture of cast and wrought aluminum pieces with very different compositions. Cast Al pieces, with their high Si, Cu and Fe content, are a major contaminant in wrought scrap fraction, which results in downcycling of the mixed cast + wrought scrap into non-structural cast Al alloys and parts. Here, in this paper, we introduce a chemical treatment method to color-code scrap aluminum pieces by alloy family and demonstrate low-cost optical sorting of cast from wrought pieces to upgrade the scrap stream. We utilized non-acidic chemical solutions that react with (i.e., etch) the scrap pieces to produce colors based on the Al alloy chemistry of a given piece. Cast pieces with high Si and Cu fractions turned black, whereas the much leaner wrought pieces remained unreacted. We showed > 95% sorting efficiency of mixed cast and wrought pieces using a repurposed low-cost optical sorter originally designed for food sorting. We also colored wrought Al pieces by alloy families, such as 5xxx and 6xxx, using a two-step chemical etching technique, which has the potential to create a circular supply chain in which wrought aluminum alloys are sorted from the mixed scrap stream and recycled back to high-value wrought products such as sheets, extrusions, and forgings with minimal contamination from cast scrap.

Aluminum↗

Influence of Pore Length on Hydrogenolysis of Polyethylene within a Mesoporous Support Architecture

Due to the plastic waste crisis, selective chemical upcycling of polyolefins into value-added products is a topic of intense interest, demanding polymer deconstruction processes that afford control over the product chain lengths. Recently, a catalytic architecture was synthesized in which a polyolefin melt infiltrates a porous support, and its chains are cleaved by a metal nanoparticle catalyst at the bottom of the pores, yielding a narrow distribution of alkane products. Although the influence of various parameters of these catalytic materials, including the effects of the nanoparticle size and pore diameter on product chain length, has been examined before, here, we investigate the role of the pore length in the cleavage process through the first study that combines catalytic hydrogenolysis and coarse-grained modeling to gain insights not available by experiment alone. We show that the pore length can permit control over the average product length with qualitative agreement between experiment and simulation. In conclusion, we go beyond this observation to uncover the dynamic phenomenon responsible for the pore-length dependence of the cleavage products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Two Mesoporous Domains Are Better Than One for Catalytic Deconstruction of Polyolefins

Catalytic hydrogenolysis of polyolefins into valuable liquid, oil, or wax-like hydrocarbon chains for second-life applications is typically accompanied by the hydrogen-wasting co-formation of low value volatiles, notably methane, that increase greenhouse gas emissions. Catalytic sites confined at the bottom of mesoporous wells, under conditions in which the pore exerts the greatest influence over the mechanism, are capable of producing less gases than unconfined sites. A new architecture was designed to emphasize this pore effect, with the active platinum nanoparticles embedded between linear, hexagonal mesoporous silica and gyroidal cubic MCM-48 silica (mSiO 2 /Pt/MCM-48). This catalyst deconstructs polyolefins selectively into ~C 20 –C 40 paraffins and cleaves C–C bonds at a rate (TOF = 4.2 ± 0.3 s –1 ) exceeding that of materials lacking these combined features while generating negligible volatile side products including methane. The time-independent product distribution is consistent with a processive mechanism for polymer deconstruction. In contrast to time- and polymer length-dependent products obtained from non-porous catalysts, mSiO 2 /Pt/MCM-48 yields a C 28 -centered Gaussian distribution of waxy hydrocarbons from polyolefins of varying molecular weight, composition, and physical properties, including low-density polyethylene, isotactic polypropylene, ultrahigh-molecular-weight polyethylene, and mixtures of multiple, post-industrial polyolefins. Here, coarse-grained simulation reveals that the porous-core architecture enables the paraffins to diffuse away from the active platinum site, preventing secondary reactions that produce gases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coulomb excitation of 80,82 Kr and a change in structure approaching N = Z = 40

Nuclei approaching N = Z = 40 are known to exhibit strongly deformed structures and are thought to be candidates for shape coexistence. In the krypton isotopes, 80,82 Kr are poorly characterized, preventing an understanding of evolving deformation approaching N = 40. The present work aims to determine electric quadrupole transition strengths and quadrupole moments of 80,82 Kr in order to better characterize their deformation. Sub-barrier Coulomb excitation was employed, impinging the isotopes of krypton on 196 Pt and 208 Pb targets. Utilizing a semiclassical description of the safe Coulomb-excitation process E 2 matrix elements could then be determined. Eleven new or improved matrix elements are determined in 80 Kr and seven in 82 Kr . The new B(E2;0$^+_1$ → 2$^+_1$ ) value in 82 Kr disagrees with the evaluated value by 3σ , which can be explained in terms of deficiencies in a previous Coulomb-excitation analysis. Conclusions: Comparison of measured Q s ( 2$^+_1$ ) and B(E2; 0$^+_1$ → 2$^+_1$ ) values indicates that neutron-deficient ( N ≤ 42 ) isotopes of krypton are closer to axial deformation than other isotopic chains in the mass region. A continuation of this trend to higher Z may result in Sr and Zr isotopes exhibiting near-axial prolate deformation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Advanced Coating Compositions and Microstructures to Improve Uptime and Operational Flexibility in Cyclic, Low-Load Thermal Utility Plants

GE, the University of Tennessee, and Oak Ridge National Laboratory collaborated from 2020 to 2023 developing two key technologies for improving the viability of fuel switching and load following in thermal utility plants: a) cost-effective weld overlay compositions for boiler tubing b) cathodic arc coatings that deliver improvements in both erosion resistance and oxidation resistance in high temperature steam for HP turbine blades The team worked through a robust, logical project map to de-risk these two technologies and advance them from TRL 3 to TRL 6. For the cost-effective weld overlay, the team developed a ferritic filler material which was fabricated at a vendor for 18% the average market cost of Inconel 625 wire, had a corrosion rate 3x lower in conditions simulating a biomass-fired superheater and 10x lower in conditions simulating a coal-fired superheater, and was fabricated into prototype overlaid tubing that passed ASME requirements including transverse bending, dye penetrant inspection, and ASTM G-76 evaluation. For the cathodic arc coatings applied to steam turbine blades, the team developed a novel composition that was successfully transferred to a qualified vendor. The vendor was able to produce coated prototypes with 4x the as-deposited erosion resistance and 10.4x the post-steam-exposure erosion resistance of the TiN coating the vendor currently applies on GE steam turbine components, without significantly increasing process cost. These coated prototypes also passed a GE inspection and showed favorable performance in high temperature erosion, nanoindentation, sliding wear, scratch adhesion, and high cycle fatigue testing. If successfully deployed by GE, it is anticipated that the technologies will enable the following: • 25%-50% increase in time between outages for both boilers and HP turbines. • 50% decrease in cost for weld overlay on a per foot basis relative to todays NiCr alloys. • Adequate oxidation resistance and erosion for HP turbine inlet steam at >620°C and >220 bar. • No need for changes in component supply chain or any notable Capital Expenditures. 5 Decreasing component cost, increasing performance, and extending time between outages represent direct value propositions to GE and their customers. For the American consumer, these objectives translate into increased grid reliability (fewer unexpected outages), decreased Levelized Cost of Electricity, and improved environmental health (low-loading/load following to accelerate penetration of renewables). The results also have implications for wear resistant tooling, wire arc additive manufacturing, more durable components for syngas cleanup, and deployment of more efficient thermochemical pathways for carbon negative fuel production

09 BIOMASS FUELS↗

Feasibility of Ocean-Based Renewable Energy in the Gulf of Mexico

This paper summarizes a comprehensive feasibility assessment of six offshore renewable energy sources in the Gulf of Mexico (GOM) to potentially provide utility-scale electricity from the Outer Continental Shelf (federal waters) and state waters to land-based grids. Overall, the primary objective is to inform future energy planning. The authors evaluated offshore wind, wave energy, tidal energy, ocean-based solar photovoltaics (PV), ocean current, and ocean thermal energy conversion. Of these energy resources, offshore wind was the most viable option and was the focus of the second part of the study. The technical challenges of developing offshore wind in the GOM are discussed including hurricane design for turbines and substructures, as well as turbine solutions to overcome lower wind regimes. In addition, advantages to offshore wind development in the GOM are described including proximity to oil and gas supply chains. Economic analysis using established cost models at the National Renewable Energy Laboratory identified hypothetical project locations where net value of offshore wind was the highest, and the levelized cost of energy (LCOE) was calculated for three sites: Port Isabel, Port Arthur, and Pensacola. Offshore wind LCOE in the GOM was found to be higher than those in sites along the north and mid-Atlantic coasts, but decreasing cost trajectories indicate the possibility of economic viability for locations in Texas and west Louisiana after 2030. The extrapolated 2030 LCOE values range from 73 dollars per MWh (Site 1, Port Isabel) and 79 dollars per MWh (Site 3, Port Arthur) to 91 dollars per MWh (Site 5, Pensacola).

16 TIDAL AND WAVE POWER↗

Intra-Specific Variability in Plant Hydraulic Parameters Inferred From Model Inversion of Sap Flux Data

Understanding plant hydraulic regulation is critical for predicting plant and ecosystem responses to projected increases in drought stress. Plant hydraulic regulation is controlled by observable, diverse plant hydraulic traits that can vary as much across individuals of the same species as they do across different species. Direct measurements of plant hydraulic traits from a range of ecosystems remain limited in comparison to other, more readily measured traits (e.g., specific leaf area). Furthermore, plant hydraulic trait measurements, often made at leaf or branch levels, are not easily scaled to whole-plant values that are typically used to predict plant and ecosystem fluxes. In this study, multiple whole-plant hydraulic parameters are inferred from observations of plant water use (i.e., sap flow), soil properties, and meteorological data. We use a Markov Chain Monte Carlo model inversion approach to obtain the best estimates and uncertainty of plant hydraulic parameters that capture whole-plant effective embolism resistance and stomatal sensitivity to decreasing plant water potential. We then use the inferred values in the model to estimate whole-tree water use and isohydricity. This approach reliably infers whole-plant parameter values with enough specificity to resolve inter- and intra-specific differences, and thus supplements time- and labor-intensive direct measurements of traits.

54 ENVIRONMENTAL SCIENCES↗

Constructing Hubbard models for the hydrogen chain using sliced-basis density matrix renormalization group

Sliced-basis DMRG(sb-DMRG) is used to simulate a chain of hydrogen atoms and to construct low-energy effective Hubbard-like models. The downfolding procedure first involves a change of basis to a set of atom-centered Wannier functions constructed from the natural orbitals of the exact DMRG one-particle density matrix. The Wannier function model is then reduced to a fewer-parameter Hubbard-like model, whose parameters are determined by minimizing the expectation value of the Wannier Hamiltonian in the ground state of the Hubbard Hamiltonian. This indirect variational procedure not only yields compact and simple models for the hydrogen chain, but also allows us to explore the importance of constraints in the effective Hamiltonian, such as the restricting the range of the single-particle hopping and two-particle interactions, and to assess the reliability of more conventional downfolding. The entanglement entropy for a model's ground state, cut in the middle, is an important property determining the ability of DMRG and tensor networks to simulate the model, and here we study its variation with the range of the interactions. Counterintuitively, we find that shorter ranged interactions often have larger entanglement.

36 MATERIALS SCIENCE↗

Bio‐based glycerol plasticizers for flexible poly(vinyl chloride) blends

Abstract A series of glycerol‐based compounds were investigated for their application as plasticizers for flexible poly(vinyl chloride) (PVC) blends. The effect of plasticizer chemical structure on the performance, migration behavior, and blend morphology were evaluated and compared to blends produced using the commercial plasticizer dioctyl terephthalate (DOTP). Blends containing 40 phr (parts per hundred rubber) of glycerol‐based plasticizer showed a considerable reduction (between 54 to 86°C) in glass transition temperature ( T g ) relative to neat PVC ( T g ~ 80°C). Tensile testing of samples prepared with the glycerol analogs demonstrated higher ductility (elongation at break values of up to 97%) than DOTP (elongation at break value of 75%) at identical plasticizer loadings. The surface morphologies showed excellent incorporation of the glycerol plasticizers functionalized with alkyl chains longer than four carbons in length into the PVC matrix, whereas droplet formation was observed in blends with shorter chain glycerol derivatives. Leaching behavior of the plasticized samples were evaluated into different media and showed that plasticizers comprised of branched, or longer alkyl chains produced 2‐ to 4‐fold lower migration rates compared to those with shorter alkyl chains into polar solutions.

Halloran, Matthew W.↗

Advancement of Actinide Metal–Organic Framework Chemistry via Synthesis of Pu-UiO-66

We report the synthesis and characterization of the first plutonium metal–organic framework (MOF). Pu-UiO-66 expands the established UiO-66 series, which includes transition metal, lanthanide, and early actinide elements in the hexanuclear nodes. The thermal stability and porosity of Pu-UiO-66 were experimentally determined, and multifaceted computational methods were used to corroborate experimental values, examine inherent defects in the framework, decipher spectroscopic signatures, and elucidate the electronic structure. The crystallization of a plutonium chain side product provides direct evidence of the competition that occurs between modulator and linker in MOF syntheses. Ultimately, the synthesis of Pu-UiO-66 demonstrates adept control of Pu(IV) coordination under hydrolysis-prone conditions, provides an opportunity to extend trends across isostructural UiO-66 frameworks, and serves as the foundation for future plutonium MOF chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Mesopore-Confined and Graphene Oxide-Localized Ruthenium Catalyst Increases Rates of Mid-Chain Polyolefin Hydrogenolysis

A catalyst architecture with mesoporous silica coating Ru nanoparticles on reduced graphene oxide (mSiO 2 /Ru/rGO) localizes the 2 nm Ru solely at the closed bottoms of 2.9 nm diameter mesopores. mSiO 2 /Ru/rGO catalyzes the rapid, selective hydrogenolysis of polyolefins at wax formation rates (ν wax ) up to 1700 g wax ·g Ru –1 ·h –1 and a turnover frequency (TOF) for C–C bond cleavage of 130 ± 8 min –1 . The ν wax and TOF for mSiO 2 /Ru/rGO are 23× and 16× those of nonporous Ru/rGO, respectively, indicating that faster chain cleavage is also more selective inside mesopores. The methane yield from mSiO 2 /Ru/rGO is ca. 30% of the value obtained from Ru/rGO. Methane decreases, and wax selectivity improves with narrow-pore (2.3 nm) mSiO 2 /Ru/rGO. The reaction rate decreases at lower and higher H 2 pressures from its maximum at 37 bar. Log(TOF)-log(P H2 ) plots reveal rates ∝ [P H2 ] 2.8 or [P H2 ] −2.0 in the lower or higher pressure ranges, respectively. Corresponding plots for Ru/C give rates ∝ [P H2 ] 1 or [P H2 ] −2.4 . Ru is hydrocarbon-covered at low pressure; thus, the higher H 2 order for mSiO 2 /Ru/rGO indicates that mesopores increase the density of cleavable unsaturated moieties on the Ru surface. The lower H 2 order on Ru/C implies a lower density of cleavable groups because saturated segments occupy a larger fraction of the Ru surface. Higher surface occupancy by the hydrocarbon reactant correlates with more methane formation. Therefore, pore confinement, narrower pore diameter in mSiO 2 /Ru/rGO, or higher H 2 pressure leads to lower methane yields. Ru nanoparticles in mSiO 2 /Ru/rGO maintain equivalent activity and selectivity over five recycling tests.

Catalysts↗

S 8 ring content in liquid sulfur determined from x-ray diffraction

The S 8 ring content in liquid sulfur has been determined from the 4.47 Å peak in the x-ray pair distribution function over the temperature range −55 °C –330 °C. This peak represents the characteristic 3rd and 4th nearest atom-atom distances across an S 8 -ring. Three procedures were used to calculate the S 8 -ring fraction; scaling to crystalline β-S, a linear combination fit and a direct integration method. All methods gave similar values, indicating that approximately one third of the S 8 -rings break up upon melting into a distribution of short chains with an average length of 5 ± 2 atoms. Our results contradict established models of low temperature sulfur that indicate below the λ-transition the liquid comprises almost entirely of S8-rings. In addition, we find the S 8 -ring fraction increases to 76 ± 10% at −30 °C in the supercooled liquid, and decreases to 23% ± 3% at 330 °C in the high temperature melt. First principle molecular dynamics calculations confirm the onset of dynamic ring distortion via broad bond angle distributions, associated with the interstitial region between the first and second peaks in the pair distribution function. Our results are consistent with the presence of a propensity of short chains in the low temperature liquid, that are required for the bond switching mechanism responsible for the polymerization process to occur at the λ-transition temperature, T λ .

lambda transition↗