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At least 1,621 records · Page 90
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Cost analysis of alternative large-scale high-temperature solid oxide electrolysis hydrogen production facilities

We extend our past cost analysis of gigawatt-scale solid oxide electrolysis (SOE) facilities that produce high purity hydrogen gas from water by estimating construction and operating costs for three new alternative design cases: (1) offsite feed steam generation; (2) near-atmospheric pressure (NAP) stack; and (3) onsite electric boiler feed steam generation. Pressure effects on hydrogen electrode-(cathode-)supported SOE cell (SOEC) stack performance are estimated for the same assumed cell and stack construction and used to determine facility-wide stack capital costs for achieving a fixed H2 production at different pressures. Modular balance of plant (BOP) process equipment capital costs are estimated for each new alternative design case using our past equipment sizing, design, and cost data and scaling relationships. Furthermore, we update BOP equipment sizing and design for the NAP case using Aspen®. Vendor quotes for electric boilers are used to estimate costs for the electric boiler design case. Factory and onsite assembly and installation costs for SOEC stacks and BOP equipment are calculated using our past simplified first-principles approach. First-of-a-kind (FOAK) and N th -of-a-kind (NOAK) production maturity cost estimates are included for all results. The case with NAP stacks offers the lowest facility total capital cost (TCC, ~23% lower than base) while use of small electric boilers requires the highest TCC (~3% higher than base). H 2 production prices decrease from the base of ~$\$2.17$ /kgH 2 to ~$\$1.92$/kgH 2 for 1 GW e DC SIP facilities utilizing NAP stacks supplied by offsites steam situated in large modules and blocks for $\$0.030$/kWh e and $0.009/kWh t prices for electricity and thermal energy, respectively. We report all costs in 2021 US dollars.

Balance of plant (BOP) process equipment↗
DOE OSTI2014

Attitudes Toward Blinding of Peer Review and Perceptions of Efficacy Within a Small Biomedical Specialty

Purpose: Peer reviewers' knowledge of author identity may influence review content, quality, and recommendations. Therefore, the International Journal of Radiation Oncology, Biology, Physics (“Red Journal”) implemented double-blinded peer review in 2011. Given the relatively small size of the specialty and the high frequency of preliminary abstract presentations, we sought to evaluate attitudes, the efficacy of blinding, and the potential impact on the disposition of submissions. Methods and Materials: In May through August 2012, all Red Journal reviewers and 1 author per manuscript completed questionnaires regarding demographics, attitudes, and perceptions of success of blinding. We also evaluated correlates of the outcomes of peer review. Results: Questionnaires were received from 408 authors and 519 reviewers (100%). The majority of respondents favored double blinding; 6% of authors and 13% of reviewers disagreed that double blinding should continue in the Red Journal. In all, 50% of the reviewers did not suspect the identity of the author of the paper that they reviewed; 19% of reviewers believed that they could identify the author(s), and 31% suspected that they could. Similarly, 23% believed that they knew the institution(s) from which the paper originated, and 34% suspected that they did. Among those who at least suspected author identity, 42% indicated that prior presentations served as a clue, and 57% indicated that literature referenced did so. Of those who at least suspected origin and provided details (n=133), 13% were entirely incorrect. Rejection was more common in 2012 than 2011, and submissions from last authors with higher H-indices (>21) were more likely to survive initial review, without evidence of interactions between submission year and author gender or H-index. Conclusions: In a relatively small specialty in which preliminary research presentations are common and occur in a limited number of venues, reviewers are often familiar with research findings and suspect author identity even when manuscript review is blinded. Nevertheless, blinding appears to be effective in many cases, and support for continuing blinding was strong.

62 RADIOLOGY AND NUCLEAR MEDICINE↗
DOE OSTI2018

Classification of machine learning frameworks for data-driven thermal fluid models

Thermal fluid processes are inherently multi-physics and multi-scale, involving mass-momentum-energy transport phenomena at multiple scales. Thermal fluid simulation (TFS) is based on solving conservative equations, for which – except for “first-principles” direct numerical simulation – closure relations (CRs) are required to provide microscopic interactions or so-called sub-grid-scale physics. In practice, TFS is realized through reduced-order modeling, and its CRs as low-fidelity models can be informed by observations and data from relevant and adequately evaluated experiments and high-fidelity simulations. This paper is focused on data-driven TFS models, specifically on their development using machine learning (ML). Five ML frameworks are introduced including physics-separated ML (PSML or Type I ML), physics-evaluated ML (PEML or Type II ML), physics-integrated ML (PIML or Type III ML), physics-recovered (PRML or Type IV ML), and physics-discovered ML (PDML or Type V ML). The frameworks vary in their performance for different applications depending on the level of knowledge of governing physics, source, type, amount and quality of available data for training. Notably, outlined for the first time in this paper, Type III models present stringent requirements on modeling, substantial computing resources for training, and high potential in extracting value from “big data” in thermal fluid research. Here the current paper demonstrates and investigates ML frameworks in three examples. First, we utilize the heat diffusion equation with a nonlinear conductivity model formulated by convolutional neural networks (CNNs) and feedforward neural networks (FNNs) to illustrate the applications of Type I, Type II, Type III, and Type V ML. The results indicate a preference for Type II ML under deficient data support. Type III ML can effectively utilize field data, potentially generating more robust predictions than Type I and Type II ML. CNN-based closures exhibit more predictability than FNN-based closures, but CNN-based closures require more training data to obtain accurate predictions. Second, we illustrate how to employ Type I ML and Type II ML frameworks for data-driven turbulence modeling using reference works. Third, we demonstrate Type I ML by building a deep FNN-based slip closure for two-phase flow modeling. The results show that deep FNN-based closures exhibit a bounded error in the prediction domain.

42 ENGINEERING↗
DOE OSTI2012

Characterization of differences in calculated and actual measured skin doses to canine limbs during stereotactic radiosurgery using Gafchromic film

Accurate calculation of absorbed dose to the skin, especially the superficial and radiosensitive basal cell layer, is difficult for many reasons including, but not limited to, the build-up effect of megavoltage photons, tangential beam effects, mixed energy scatter from support devices, and dose interpolation caused by a finite resolution calculation matrix. Stereotactic body radiotherapy (SBRT) has been developed as an alternative limb salvage treatment option at Colorado State University Veterinary Teaching Hospital for dogs with extremity bone tumors. Optimal dose delivery to the tumor during SBRT treatment can be limited by uncertainty in skin dose calculation. The aim of this study was to characterize the difference between measured and calculated radiation dose by the Varian Eclipse (Varian Medical Systems, Palo Alto, CA) AAA treatment planning algorithm (for 1-mm, 2-mm, and 5-mm calculation voxel dimensions) as a function of distance from the skin surface. The study used Gafchromic EBT film (International Specialty Products, Wayne, NJ), FilmQA analysis software, a limb phantom constructed from plastic water Trade-Mark-Sign (fluke Biomedical, Everett, WA) and a canine cadaver forelimb. The limb phantom was exposed to 6-MV treatments consisting of a single-beam, a pair of parallel opposed beams, and a 7-beam coplanar treatment plan. The canine forelimb was exposed to the 7-beam coplanar plan. Radiation dose to the forelimb skin at the surface and at depths of 1.65 mm and 1.35 mm below the skin surface were also measured with the Gafchromic film. The calculation algorithm estimated the dose well at depths beyond buildup for all calculation voxel sizes. The calculation algorithm underestimated the dose in portions of the buildup region of tissue for all comparisons, with the most significant differences observed in the 5-mm calculation voxel and the least difference in the 1-mm voxel. Results indicate a significant difference between measured and calculated data extending to average depths of 2.5 mm, 3.4 mm, and 10 mm for the 1-mm, 2-mm, and 5-mm dimension calculation matrices, respectively. These results emphasize the importance of selecting as small a treatment planning software calculation matrix dimension as is practically possible and of taking a conservative approach for skin treatment planning objectives. One suggested conservative approach is accomplished by defining the skin organ as the outermost 2-3 mm of the body such that the high dose tail of the skin organ dose-volume histogram curve represents dose on the deep side of the skin where the algorithm is more accurate.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2019

In situ polymerized succinonitrile-based solid polymer electrolytes for lithium ion batteries

Novel solid polymer electrolytes based on succinonitrile (SN) plastic crystal electrolyte (SN-PCE) and polymerized ionic liquid (PIL) has been successfully synthesized via an in-situ method. The fabricated electrolyte (PIL-SN-PCE) is uniformly inlayed into the supporting matrix of polyimide, which effectively ameliorates the mechanical properties of the electrolyte. PIL can effectively enhance the thermal stability of electrolytes up to 300 °C and mitigate the parasitic reactions between the electrolytes and the electrodes. PIL-SN-PCE exhibits a remarkable oxidation ability up to 5.4 V vs Li/Li + and a high room temperature ionic conductivity of 6.54 × 10 -4 S cm -1 . Furthermore, in-situ formed interface in PIL-SN-PCE guarantee an excellent compatibility with different electrodes, which can effectively improve the cycle stability and rate performances of both half-cells and full cells. Finally, PIL-SN-PCE is considered as a promising electrolyte for high energy density lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2013

7,12-Dimethylbenz[a]anthracene exposure induces the DNA repair response in neonatal rat ovaries

7,12-Dimethylbenz[a]anthracene (DMBA) destroys ovarian follicles at all stages of development. This study investigated DMBA-induced DNA double strand break (DSB) formation with subsequent activation of the ovarian DNA repair response in models of pre-antral or pre-ovulatory follicle loss. Postnatal day (PND) 4 Fisher 344 (F344) rat ovaries were cultured for 4 days followed by single exposures of vehicle control (1% DMSO) or DMBA (12.5 nM or 75 nM) and maintained in culture for 4 or 8 days. Alternately, PND4 F344 rat ovaries were exposed to 1 μM DMBA at the start of culture for 2 days. Total RNA or protein was isolated, followed by qPCR or Western blotting to quantify mRNA or protein level, respectively. γH2AX and phosphorylated ATM were localized and quantified using immunofluorescence staining. DMBA exposure increased caspase 3 and γH2AX protein. Additionally, DMBA (12.5 nM and 1 μM) increased levels of mRNA encoding Atm, Xrcc6, Brca1 and Rad51. In contrast, Parp1 mRNA was decreased on d4 and increased on d8 of DMBA exposure, while PARP1 protein increased after 8 days of DMBA exposure. Total ATM increased in a concentration-dependent temporal pattern (75 nM d4; 12.5 nM d8), while pATM was localized in large primary and secondary follicles and increased after 8 days of 75 nM DMBA exposure compared to both control and 12.5 nM DMBA. These findings support that, despite some concentration effects, DMBA induces ovarian DNA damage and that DNA repair mechanisms are induced as a potential mechanism to prevent follicle loss. - Highlights: • DMBA exposure increases ovarian caspase-3 protein expression. • DMBA exposure increases the γH2AX protein in oocytes. • DMBA exposure activates a DNA repair response in the ovary.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

NF-κB-dependent transcriptional upregulation of cyclin D1 exerts cytoprotection against hypoxic injury upon EGFR activation

Apoptosis of neural cells is one of the main pathological features in hypoxic/ischemic brain injury. Nuclear factor-κB (NF-κB) might be a potential therapeutic target for hypoxic/ischemic brain injury since NF-κB has been found to be inactivated after hypoxia exposure, yet the underlying molecular mechanisms of NF-κB inactivation are largely unknown. Here we report that epidermal growth factor receptor (EGFR) activation prevents neuron-like PC12 cells apoptosis in response to hypoxia via restoring NF-κB-dependent transcriptional upregulation of cyclin D1. Functionally, EGFR activation by EGF stimulation mitigates hypoxia-induced PC12 cells apoptosis in both dose- and time-dependent manner. Of note, EGFR activation elevates IKKβ phosphorylation, increases IκBα ubiquitination, promotes P65 nuclear translocation and recruitment at cyclin D1 gene promoter as well as upregulates cyclin D1 expression. EGFR activation also abrogates the decrease of IKKβ phosphorylation, reduction of IκBα ubiquitination, blockade of P65 nuclear translocation and recruitment at cyclin D1 gene promoter as well as downregulation of cyclin D1 expression induced by hypoxia. Furthermore, NF-κB-dependent upregulation of cyclin D1 is instrumental for the EGFR-mediated cytoprotection against hypoxic apoptosis. In addition, the dephosphorylation of EGFR induced by either EGF siRNA transfection or anti-HB-EGF neutralization antibody treatment enhances hypoxic cytotoxicity, which are attenuated by EGF administration. Our results highlight the essential role of NF-κB-dependent transcriptional upregulation of cyclin D1 in EGFR-mediated cytoprotective effects under hypoxic preconditioning and support further investigation of EGF in clinical trials of patients with hypoxic/ischemic brain injury. - Highlights: • EGFR activation significantly decreases hypoxia-induced PC12 cells injury. • EGFR activation abrogates the transcriptional repression of cyclin D1 induced by hypoxia in a NF-κB-dependent manner. • NF-κB-dependent cyclin D1 upregulation is required for the EGFR-mediated cytoprotection against hypoxia-induced injury. • Endogenous EGFR activity antagonizes hypoxia-induced PC12 cells injury.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2025

Assessment of integral models for non-Boussinesq lazy plumes using numerical simulations

Integral modelling of turbulent buoyant plumes is crucial for rapid predictions of plume characteristics. While the governing equations are typically derived using self-similarity and a Boussinesq approximation, these assumptions may not hold for plumes originating from finite-area sources with large density ratios. Here, this work evaluates the accuracy of integral-scale models for non-Boussinesq lazy plumes using high-fidelity numerical simulations of turbulent helium plumes. We analyse the plume kinematics by computing vertical fluxes, plume radius and radial profiles, establishing some disparities between common practice and physical accuracy. We identify how the definition of the plume radius changes the perception of the plume structure when the flow is not self-similar and derive a relationship between the flux-based and threshold-based definitions without requiring self-similarity. We then examine the plume dynamics by evaluating the source terms from the governing plume equations. Our results support neglecting diffusive and viscous effects but emphasise the importance of the mean pressure gradient, even in the self-similar regime. Two coefficients need to be modelled: the well-known entrainment coefficient and the lesser-known momentum correction coefficient, which is a correction required for the momentum equation to account for self-similar and slender approximations. The momentum correction coefficient is found to be approximately constant and slightly greater than the assumed value of 1. The standard entrainment coefficient models perform well up to a local Richardson number three times the asymptotic value but overpredict entrainment for larger Richardson numbers. We propose a correction using the known finite limit of entrainment at infinite Richardson number.

Meehan, Michael Alexander [Sandia National Laborat↗
DOE OSTI2022

Methane Catalytic Pyrolysis by Microwave and Thermal Heating over Carbon Nanotube-Supported Catalysts: Productivity, Kinetics, and Energy Efficiency

Methane catalytic pyrolysis, which is the reaction to produce hydrogen and carbon without emitting CO 2 , represents an approach for decarbonization using natural gas as an energy resource. In this work, the endothermic pyrolysis reaction was carried out under two heating scenarios: convective thermal heating and microwave-driven irradiative heating. The pyrolysis reaction was conducted at 550-600 °C over carbon nanotube-supported Ni-Pd and Ni-Cu catalysts. On both catalysts, an enhanced methane conversion rate was observed under microwave irradiation. The enhanced catalytic activity was hypothetically caused by the presence of free electrons in the carbon atoms within CNT that enabled the CNT support to absorb microwave energy effectively and to be heated efficiently by microwave. The microwave catalytic pyrolysis has shown improvement in kinetics, where the apparent activation energy dropped from 45.5 kJ/mol under conventional convective heating to 24.8 kJ/mol under microwave irradiation. When the methane conversion rate is increased by 37 %, the microwave power consumption only changed by 10.8 %. The research demonstrated the potential of transforming natural gas to clean hydrogen and value-added carbon in a more energy-efficient way. Process simulation and techno-economic analysis showed that potentially hydrogen minimum selling price of about $1 /kg H 2 could be achieved.

03 NATURAL GAS↗
DOE OSTI2016

Hydrodeoxygenation of p -Cresol over Pt/Al 2 O 3 Catalyst Promoted by ZrO 2 , CeO 2 , and CeO 2 –ZrO 2

ZrO 2 -Al 2 O 3 and CeO 2 -Al 2 O 3 were prepared by a co-precipitation method and selected as supports for Pt catalysts. The effects of CeO 2 and ZrO 2 on the surface area and Brønsted acidity of Pt/Al 2 O 3 were studied. In the hydrodeoxygenation (HDO) of p-cresol, the addition of ZrO 2 promoted the direct deoxygenation activity on Pt/ZrOO 2 -Al 2 O 3 via Caromatic-O bond scission without benzene ring saturation. Pt/CeOO 2 -Al 2 O 3 exhibited higher deoxygenation extent than Pt/Al 2 O 3 due to the fact that Brønsted acid sites on the catalyst surface favored the adsorption of p-cresol. With the advantages of CeO 2 and ZrO 2 taken into consideration, CeO 2 -ZrOO 2 -Al 2 O 3 was prepared, leading to the highest HDO activity of Pt/CeO 2 -ZrOO 2 -Al 2 O 3 . The deoxygenation extent for Pt/CeO 2 -ZrOO 2 -Al 2 O 3 was 48.4% and 14.5% higher than that for Pt/ZrO2O 2 -Al 2 O 3 and Pt/CeOO 2 -Al 2 O 3 , respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Theoretical Modeling of 99 Tc NMR Chemical Shifts

Technetium (Tc) displays a rich chemistry due to the wide range of oxidation states (from -I to +VII) and ability to form coordination compounds. Determination of Tc speciation in complex mixtures is a major challenge, and 99Tc NMR spec-troscopy is widely used to probe chemical environments of Tc in odd oxidation states. However interpretation of the 99Tc NMR data is hindered by the lack of reference compounds. DFT computations can help fill this gap, but to date few com-putational studies have focused on 99Tc NMR of compounds and complexes. This work systematically evaluates the inclu-sion small percentages of Hartree-Fock exchange correlation and relativistic effects in DFT computations to support in-terpretation of the 99Tc NMR spectra. Hybrid functionals are found to perform better than their pure GGA counterparts, and non-relativistic calculations have been found to generally show a lower mean absolute deviation from experiment. Overall non-relativistic PBE0 and B3PW91 calculations are found to most accurately predict 99Tc NMR chemical shifts.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2025

In Situ Studies of Copper-Zirconia-Zinc Oxide Model Catalysts for CO 2 Hydrogenation

A combination of in situ X-ray photoelectron spectroscopy (XPS) and infrared reflection absorption spectroscopy (IRAS) was used to investigate the formation of surface intermediates from CO 2 hydrogenation on copper-zirconia-zinc oxide model catalysts under reaction conditions. Copper clusters with different numbers of atoms (n = 1, 4, 13) were deposited onto bare and ZrO 2 -modified ZnO powder supports to systematically examine the effects of Cu cluster size and the synergy between metal and metal-oxide components. Under low pressure CO 2 hydrogenation conditions (CO 2 :H 2 = 1:9, 0.4 mbar, 300–600 K), XPS and IRAS identify the most prominent intermediates as carbonate (CO 3 *), formate (HCOO*) and methoxy (CH 3 O*), which is the final surface-bound intermediate leading to methanol. The temperature profiles are consistent with a mechanism in which CO 2 is adsorbed as carbonate species (HCO 3 *, CO 3 *) followed by hydrogenation reactions to formate (HCOO*) and methoxy (CH 3 O*), but the relative yields strongly depend on surface composition. Specifically, the presence of ZrO 2 promotes CO 2 adsorption and activation and improves the thermal stability of the Cu clusters against loss of surface area. Moreover, the ternary Cu 4 /ZrO 2 /ZnO surface is significantly more active than Cu 4 /ZnO and ZrO 2 /ZnO surfaces for the formation of methoxy (CH 3 O*), indicating that Cu–ZrO 2 interfaces promote the formation of key intermediates leading to methanol. Finally, the yields of intermediates are similar for all Cu cluster sizes (Cu 1 , Cu 4 and Cu 13 ), indicating that the primary role of Cu is to provide H atoms via H 2 dissociation and spillover. In conclusion, these molecular-level insights provide a fundamental understanding of the enhanced efficiency of ternary Cu–ZrO 2 –ZnO catalysts and establish design principles for developing improved catalysts for CO 2 conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Nearby Sites Show Similar Upwind Sources and Differing Semivolatile Concentrations in Coastal Aerosol Particles

The Eastern Pacific Cloud Aerosol Precipitation Experiment (EPCAPE) characterized aerosol composition using measurements at two sites within 3 km (Scripps Pier and Mt. Soledad) from 15 February 2023 to 14 February 2024. Comparing the two sites shows the strong influence of upwind sources that results in similar monthly compositions at both sites. The seasonal changes in chemical mass concentrations were largely driven by the upwind source regions, with coastal northwesterly back-trajectories occurring 63−65% of the year and bringing submicrometer mass concentrations that were lower than the EPCAPE average for all trajectories at each site. In contrast, refractory black carbon (rBC) and nonrefractory (NR)-organics and nitrate mass concentrations exceeded EPCAPE average concentrations for back-trajectories from urban areas such as Los Angeles-Long Beach. For hourly measurements, NR-organics and non-sea-salt (NSS)-sulfate mass concentrations at Mt. Soledad were correlated strongly (r = 0.73−0.82) to those measured at Scripps Pier, but NR-nitrate was correlated only moderately (r = 0.63). The explanation for the lower correlation of NR-nitrate is both emissions between the sites and semivolatility, with semivolatility accounting for site-to-site changes in daily averages of +0.01 μg m −3 per percentage site-to-site difference in relative humidity and −0.07 μg m −3 per degree Celsius site-to-site difference in temperature. On average, comparing Scripps Pier to Mt. Soledad, NR-nitrate was higher by 29% because of relative humidity and lower by −26% because of temperature. NR-nitrate and rBC mass concentrations at Scripps Pier for nighttime were 13−15% higher than those for daytime because land breezes brought higher inland concentrations. Concentrations of rBC were 52% higher at Mt. Soledad than those measured at Scripps Pier, accompanied by increases in tracers for brake wear because of traffic on the steep roads within 10 m of that site. The implications are that these nearby sites had comparable monthly concentrations of measured components due to their similar backtrajectories, but hourly and daily concentration differences supported quantification of the meteorological effects from relative humidity and temperature on semivolatile NR-nitrate as well as minor differences from land−sea breezes and local emissions.

Aerosols↗
DOE OSTI2026

Electronic Band Structures of a Germanium Halide Perovskite Semiconductor

CsGeX 3 , a class of halide perovskites, is an emergent semiconductor with ferroelectricity and potential optoelectronic properties that can be harnessed for device applications. However, measurements of the electronic structure for this class of material are still lacking. Here, in this work, we report, for the first time, the experimental band structures of CsGeI 3 , a ferroelectric halide perovskite semiconductor, through angle-resolved photoemission spectroscopy (ARPES). The crystals were cleaved along both the (110) and (111) surfaces, facilitating the observation of clear valence band dispersions in several high-symmetry momentum directions. The observed valence band is characterized by a small hole effective mass of ∼0.1m 0 at the valence band maximum, without notable spectral signatures associated with the Rashba effect. Our experimental measurements are supported by electronic structure calculations in the DFT + G0W0 framework, enabling assessment of the band orbital characteristics, dispersion, and spin-splitting. This work unveils the intrinsic electronic and transport properties of CsGeX 3 , thereby advancing the optimization of the optoelectronic properties of this class of materials.

angle-resolved photoemission spectroscopy↗
DOE OSTI2024

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↗
DOE OSTI2020

Nature of Reactive Hydrogen for Ammonia Synthesis over a Ru/C12A7 Electride Catalyst

Recently, there have been renewed interests in exploring new catalysts for ammonia synthesis under mild conditions. Electride-based catalysts are among the emerging ones. Ruthenium particles supported on an electride composed of a mixture of calcium and aluminum oxides (C12A7) have attracted great attention for ammonia synthesis due to their facile ability in activating N2 under ambient pressure. However, the exact nature of the reactive hydrogen species and the role of electride support still remain elusive for this catalytic system. Here, we report for the first time that the surface-adsorbed hydrogen, rather than the hydride encaged in the C12A7 electride, plays a major role in ammonia synthesis over the Ru/C12A7 electride catalyst with the aid of in situ neutron scattering techniques. Combining in situ neutron diffraction, inelastic neutron spectroscopy, density functional theory (DFT) calculation, and temperature-programmed reactions, the results provide direct evidence for not only the presence of encaged hydrides during ammonia synthesis but also the strong thermal and chemical stability of the hydride species in the Ru/C12A7 electride. Steady state isotopic transient kinetic analysis (SSITKA) of ammonia synthesis showed that the coverage of reactive intermediates increased significantly when the Ru particles were promoted by the electride form (coverage up to 84%) of the C12A7 support rather than the oxide form (coverage up to 15%). Such a drastic change in the intermediate coverage on the Ru surface is attributed to the positive role of electride support where the H2 poisoning effect is absent during ammonia synthesis over Ru. The finding of this work has significant implications for understanding catalysis by electride-based materials for ammonia synthesis and hydrogenation reactions in general.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Identification and Catalysis of the Potential-Limiting Step in Lithium-Sulfur Batteries

The Li-S chemistry is thermodynamically promising for high-density energy storage but kinetically challenging. Over the past few years, many catalyst materials have been developed to improve the performance of Li-S batteries and their catalytic role has been increasingly accepted. However, the classic catalytic behavior, i.e., reduction of reaction barrier, has not been clearly observed. Crucial mechanistic questions, including what specific step is limiting the reaction rate, whether/how it can be catalyzed, and how the catalysis is sustained after the catalyst surface is covered by solid products, remain unanswered. Herein, we report the first identification of the potential-limiting step of Li-S batteries operating under lean electrolyte conditions and its catalysis that conforms to classic catalysis principles, where the catalyst lowers the kinetic barrier of the potential-limiting step and accelerates the reaction without affecting the product composition. After carefully examining the electrochemistry under lean electrolyte conditions, we update the pathway of the Li-S battery reaction: S 8 solid is first reduced to Li 2 S 8 and Li 2 S 4 molecular species sequentially; the following reduction of Li 2 S 4 to a Li 2 S 2 -Li 2 S solid with an almost constant ratio of 1:4 is the potential-limiting step; the previously believed Li 2 S 2 -to-Li 2 S solid-solid conversion does not occur; the recharging reaction is relatively fast. We further demonstrate that supported cobalt phthalocyanine molecules can effectively catalyze the potential-limiting step. After Li 2 S 2 /Li 2 S buries the active sites, it can self-catalyze the reaction and continue driving the discharging process.

25 ENERGY STORAGE↗
DOE OSTI2024

Metal-Tuned Ligand Reactivity Enables CX 2 (X = O, S) Homocoupling with Spectator Cu Centers

Ligand non-innocence is ubiquitous in catalysis with ligands in synthetic complexes contributing as electron reservoirs or co-sites for substrate activation. The latter chemical non-innocence is manifested in H + storage or relay at sites beyond the metal primary coordination sphere. Reaction of a competent CO 2 -to-oxalate reduction catalyst, namely, [K(THF) 3 ](Cu 3 SL), where L 3– is a tris(β-diketiminate) cyclophane, with CS 2 affords tetrathiooxalate at long reaction times or at high CS 2 concentrations, where otherwise an equilibrium is established between the starting species and a complex–CS 2 adduct in which the CS 2 is bound to the C atom on the ligand backbone. X-ray diffraction analysis of this adduct reveals no apparent metal participation, suggesting an entirely ligand-based reaction controlled by the charge state of the cluster. Here, thermodynamic parameters for the formation of the aforementioned Cligand–CS 2 bond were experimentally determined, and trends with cation Lewis acidity were studied, where more acidic cations shift the equilibrium toward the adduct. Relevance of such an adduct in the reduction of CO 2 to oxalate by this complex is supported by DFT studies, similar effects of countercation Lewis acidity on product formation, and the homocoupled heterocumulene product speciation as determined by isotopic labeling studies. Taken together, this system extends chemical non-innocence beyond H + to effect catalytic transformations involving C–C bond formation and represents the rarest example of metal–ligand cooperativity, that is, spectator metal ion(s) and the ligand as the reaction center.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗