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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Search for resonant pair production of Higgs bosons in the $\textrm{b}\overline{\textrm{b}}\textrm{b}\overline{\textrm{b}}$ final state using large-area jets in proton-proton collisions at $\sqrt{s}$ = 13 TeV

A search is presented for the resonant production of a pair of standard model-like Higgs bosons using data from proton-proton collisions at a centre-of-mass energy of 13 TeV, collected by the CMS experiment at the CERN LHC in 2016–2018, corresponding to an integrated luminosity of 138 fb −1 . The final state consists of two b quark-antiquark pairs. The search is conducted in the region of phase space where at least one of the pairs is highly Lorentz-boosted and is reconstructed as a single large-area jet. The other pair may be either similarly merged or resolved, the latter reconstructed using two b-tagged jets. The data are found to be consistent with standard model processes and are interpreted as 95% confidence level upper limits on the product of the cross sections and the branching fractions of the spin-0 radion and the spin-2 bulk graviton that arise in warped extradimensional models. The limits set are in the range 9.74–0.29 fb and 4.94–0.19 fb for a narrow radion and a graviton, respectively, with masses between 1 and 3 TeV. For a radion and for a bulk graviton with widths 10% of their masses, the limits are in the range 12.5–0.35 fb and 8.23–0.23 fb, respectively, for the same masses. These limits result in the exclusion of a narrow-width graviton with a mass below 1.2 TeV, and of narrow and 10%-width radions with masses below 2.6, and 2.9 TeV, respectively.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Search for heavy neutral resonances decaying to tau lepton pairs in proton-proton collisions at $\sqrt{s}$=13 TeV

A search for heavy neutral gauge bosons (𝑍′) decaying into a pair of tau leptons is performed in proton-proton collisions at $\sqrt{s}$ =13 TeV at the CERN LHC. The data were collected with the CMS detector and correspond to an integrated luminosity of 138 fb −1 . The observations are found to be in agreement with the expectation from standard model processes. Limits at 95% confidence level are set on the product of the 𝑍′ production cross section and its branching fraction to tau lepton pairs for a range of 𝑍′ boson masses. For a narrow resonance in the sequential standard model scenario, a 𝑍′ boson with a mass below 3.5 TeV is excluded. This is the most stringent limit to date from this type of search.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Amplitude analysis and branching-fraction measurement of ${D}_s^{+}\to {K}_S^0{\pi}^{+}{\pi}^0$

By using 6.32 fb -1 of data collected with the BESIII detector at center-of-mass energies between 4.178 and 4.226 GeV, we perform an amplitude analysis of the decay $D^+_s$→$K^0_Sπ^+π^0$ and determine the relative fractions and phase differences of different intermediate processes, which include $K^0_Sρ$(770) + ,$K^0_Sρ$(1450) + , $K^*$(892)$^0π^+$, $K^*$(892)$^+π^0$, and $K^*$(1410)$^0π^+$. With the detection efficiency based on the amplitude analysis results, the absolute branching fraction is measured to be $\mathcal{B}$($D^+_s$→$K^0_Sπ^+π^0$)=(5.43±0.30 stat ±0.15 syst )×10 -3 .

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2021

Measurements of branching fractions and asymmetry parameters of $ {\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0} $, $ {\Xi}_c^0\to {\Sigma}^0{\overline{K}}^{\ast 0} $, and $ {\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast -} $ decays at Belle

Using a data sample of 980 fb -1 collected with the Belle detector at the KEKB asymmetric-energy e + e - collider, we study the processes of ${\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0}$, ${\Xi}_c^0\to {\Sigma}^0{\overline{K}}^{\ast 0}$, and ${\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast -}$ for the first time. The relative branching ratios to the normalization mode of ${\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}$ are measured to be ${\displaystyle \begin{array}{c}\mathcal{B}\left({\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0}\right)/\mathcal{B}\left({\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}\right)=0.18\pm 0.02\left(\mathrm{stat}.\right)\pm 0.01\left(\mathrm{syst}.\right),\\ {}\mathcal{B}\left({\Xi}_c^0\to {\Sigma}^0{\overline{K}}^{\ast 0}\right)/\mathcal{B}\left({\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}\right)=0.69\pm 0.03\left(\mathrm{stat}.\right)\pm 0.03\left(\mathrm{syst}.\right),\\ {}\mathcal{B}\left({\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast -}\right)/\mathcal{B}\left({\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}\right)=0.34\pm 0.06\left(\mathrm{stat}.\right)\pm 0.02\left(\mathrm{syst}.\right),\end{array}}$ where the uncertainties are statistical and systematic, respectively. We obtain ${\displaystyle \begin{array}{c}\mathcal{B}\left({\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0}\right)=\left(3.3\pm 0.3\left(\mathrm{stat}.\right)\pm 0.2\left(\mathrm{syst}.\right)\pm 1.0\left(\mathrm{ref}.\right)\right)\times {10}^{-3},\\ {}\mathcal{B}\left({\Xi}_c^0\to {\Sigma}^0{\overline{K}}^{\ast 0}\right)=\left(12.4\pm 0.5\left(\mathrm{stat}.\right)\pm 0.5\left(\mathrm{syst}.\right)\pm 3.6\left(\mathrm{ref}.\right)\right)\times {10}^{-3},\\ {}\mathcal{B}\left({\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast 0}\right)=\left(6.1\pm 1.0\left(\mathrm{stat}.\right)\pm 0.4\left(\mathrm{syst}.\right)\pm 1.8\left(\mathrm{ref}.\right)\right)\times {10}^{-3},\end{array}}$ where the uncertainties are statistical, systematic, and from $\mathcal{B}\left({\Xi}_c^0\to {\Xi}^{-}{\pi}^{+}\right)$, respectively. The asymmetry parameters $\alpha \left({\Xi}_c^0\to \Lambda {\overline{K}}^{\ast 0}\right)$ and $\alpha \left({\Xi}_c^0\to {\Sigma}^{+}{K}^{\ast -}\right)$ are 0.15 ± 0.22(stat.) ± 0.04(syst.) and -0.52 ± 0.30(stat.) ± 0.02(syst.), respectively, where the uncertainties are statistical followed by systematic.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Amplitude analysis and branching fraction measurement of the decay $\mathrm{D}_s^+$ → $\mathrm{K}^+π^+π^-π^0$

The singly Cabibbo-suppressed decay D$^+_s$ → K + π + π - π 0 is observed by using a data set corresponding to an integrated luminosity of 6.32 fb -1 recorded by the BESIII detector at the centre-of-mass energies between 4.178 and 4.226 GeV. The first amplitude analysis of D$^+_s$ → K + π + π - π 0 reveals the sub-structures in this decay and determines the fractions and relative phases of different intermediate processes. The dominant intermediate process is D$^+_s$ → K *0 ρ + , with a fit fraction of (40.5 ± 2.8 stat. ± 1.5 syst. )%. With the detection efficiency based on our amplitude analysis, the absolute branching fraction for D$^+_s$ → K + π + π - π 0 is measured to be (9.75 ± 0.54 stat. ± 0.17 syst. ) x 10 -3 .

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2026

Valorization of waste polyolefins to butene, unsaturated fatty alcohols, and branched alkenes using CO 2 and plasma catalyst

Butene, branched alkenes, and short-chain unsaturated fatty alcohols are among the chemicals that have a wide range of industrial applications in the production of fuels, chemicals, and polymers. In this work, we produced these valuable commodity chemicals from waste plastics using a single-step plasma-catalytic process at atmospheric pressure CO 2 . The study shows that combining non-thermal plasma and zeolite could convert polyolefins at a temperature of 200 °C within 15 minutes, producing liquids rich in C 5 and C 6 branched alkenes and C 6 -C 8 unsaturated fatty alcohols. Additionally, gaseous products include a high yield of butene. Comparative studies indicate that combining CO 2 plasma with zeolite synergistically increases reaction rates and alters product compositions. Product selectivity was strongly dependent on reaction conditions, including plasma power, gas flow rates, reactor temperature, and catalyst loading. Furthermore, this process was applicable to common polyolefins and post-consumer polyethylene, indicating that the plasma catalytic approach has promising potential to valorize waste plastics and greenhouse gas CO 2 into versatile chemicals.

42 ENGINEERING↗
DOE OSTI2020

Origin of Large Meteoritic SiC Stardust Grains in Metal-rich AGB Stars

Stardust grains that originated in ancient stars and supernovae are recovered from meteorites and carry the detailed composition of their astronomical sites of origin. We present evidence that the majority of large (μm-sized) meteoritic silicon carbide (SiC) grains formed in C-rich asymptotic giant branch (AGB) stars that were more metal-rich than the Sun. In the framework of the slow neutron captures (the s process) that occur in AGB stars, the lower-than-solar $^{88}$Sr/$^{86}$Sr isotopic ratios measured in the large SiC grains can only be accompanied by Ce/Y elemental ratios that are also lower than solar and predominately observed in metal-rich barium stars—the binary companions of AGB stars. Such an origin suggests that these large grains represent the material from high-metallicity AGB stars needed to explain the s-process nucleosynthesis variations observed in bulk meteorites. In the outflows of metal-rich, C-rich AGB stars, SiC grains are predicted to be small (≃0.2 μm); large (≃μm-sized) SiC grains can grow if the number of dust seeds is 2–3 orders of magnitude lower than the standard value of 10 -13 times the number of H atoms. We therefore predict that with increasing metallicity, the number of dust seeds might decrease, resulting in the production of larger SiC grains.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Study of the f 0 ( 980 ) and f 0 ( 500 ) Scalar Mesons through the Decay D s + → π + π − e + ν e

Using e + e − collision data corresponding to an integrated luminosity of 7.33 fb − 1 recorded by the BESIII detector at center-of-mass energies between 4.128 and 4.226 GeV, we present an analysis of the decay D s + → π + π − e + ν e , where the D s + is produced via the process e + e − → D s * ± D s ∓ . We observe the f 0 ( 980 ) in the π + π − system and the branching fraction of the decay D s + → f 0 ( 980 ) e + ν e with f 0 ( 980 ) → π + π − measured to be ( 1.72 ± 0.1 3 stat ± 0.1 0 syst ) × 10 − 3 , where the uncertainties are statistical and systematic, respectively. The dynamics of the D s + → f 0 ( 980 ) e + ν e decay are studied with the simple pole parametrization of the hadronic form factor and the Flatté formula describing the f 0 ( 980 ) in the differential decay rate, and the product of the form factor f + f 0 ( 0 ) and the c → s Cabibbo-Kobayashi-Maskawa matrix element | V c s | is determined for the first time to be f + f 0 ( 0 ) | V c s | = 0.504 ± 0.01 7 stat ± 0.03 5 syst . Furthermore, the decay D s + → f 0 ( 500 ) e + ν e is searched for the first time but no signal is found. The upper limit on the branching fraction of D s + → f 0 ( 500 ) e + ν e , f 0 ( 500 ) → π + π − decay is set to be 3.3 × 10 − 4 at 90% confidence level. Published by the American Physical Society 2024

Ablikim, M.↗
DOE OSTI2025

Direct measurements for the kinetics of C–C bond fission in the high temperature decomposition of isopropanol

The thermal decomposition of isopropanol was studied experimentally and theoretically with a view to isolate and directly measure rate coefficients for the dominant radical channel in this multi-channel process. Two complementary shock tube methods, laser schlieren densitomtery and H-atom atomic resonance absorption spectroscopy, were used to obtain rate coefficents for the C–C bond fission channel. The experimental ranges span temperatures from 1200–2100 K and pressures between 30–690 torr. These are the most direct measurements of this rate coefficent in the fall-off regime of relevance to high-temperature reacting systems. Theoretical studies also performed in this work confirm that the title reaction and a molecular elimination involving dehydration were the sole unimolecular processes at high temperatures. A master equation analysis yielded k ( T, P ) for the C–C fission and these are shown to be in good agreement with the present experimental measurements. Comparisons with prior experimental and theoretical studies in the literature indicate branching ratios as well as absolute k ( T, P ) for C–C bond-fission have been under-predicted for this decomposition reaction. Consequently, results from the present studies place an increased emphasis on radical-driven secondary processes in high-temperature pyrolysis of this simplest secondary alcohol.

Kim, John H. [Univ. of Michigan, Ann Arbor, MI (Un↗
DOE OSTI2025

Interplay between Mixed and Pure Exciton States Controls Singlet Fission in Rubrene Single Crystals

Singlet fission (SF) is a multielectron process in which one singlet exciton S converts into a pair of separated triplet excitons T. SF is widely studied as it may help overcome the Shockley−Queisser efficiency limit for semiconductor photovoltaic cells. To elucidate and control the SF mechanism, great attention has been given to the identification of intermediate states in SF materials, which often appear elusive due to the complexity and fast time scales of the SF process. Here, we apply 14 fs-1 ms transient absorption techniques to high-purity rubrene single crystals to disentangle the intrinsic fission dynamics from the effects of defects and grain boundaries and to identify reliably the fission intermediates. Our data demonstrates that above-gap excitation directly generates a hybrid vibronically assisted mixture of singlet state and triplet-pair multiexciton [S/TT], which rapidly (<100 fs) and coherently branches into pure singlet or triplet excitations. The relaxation of [S/TT] to S is followed by a relatively slow and temperature-activated (48 meV activation energy) incoherent fission process. The SF competing pathways and intermediates revealed here unify the observations and models presented in previous studies of SF in rubrene and offer alternative strategies for the development of SF-enhanced photovoltaic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Investigation of Low-Energy Lattice Dynamics and Their Role in Superionic Na Diffusion and Ultralow Thermal Conductivity of Na 3 PSe 4 as a Solid-State Electrolyte

The atomic dynamics of Na 3 PSe 4 were investigated using a combination of neutron scattering experiments and ab initio and machine-learned molecular dynamics simulations to probe the interplay of fast ionic diffusion with atomic vibrations (phonons) of the host lattice. Our results reveal the existence of low-energy vibrational modes, simultaneously involving motions of Na + ions and framework polyanion subunits, and show that these modes become strongly overdamped in the superionic regime as they couple with the Na + hopping process. In particular, the Na+ migration energy landscape is strongly impacted by low-energy phonons derived from a soft acoustic branch of the host lattice, which modulates the diameter of the Na + diffusion channel at the bottleneck. We find that an additional factor for the enhanced Na + conductivity in Na 3 PSe 4 is the presence of Na-vacancies, which also affect the low-frequency dynamics and thermal vibration amplitudes, pointing to an interplay between Na + vacancies and host dynamics, jointly enhancing ionic diffusivity. Finally, we investigate the origin of ultralow thermal conductivities in Na 3 PSe 4 and Na 3 PS 4 using Green–Kubo simulations and find that low-energy acoustic phonon modes of the overall crystal framework provide a dominant contribution to the thermal conductivity.

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

Search for η c ( 2 S ) → ω ω and ω ϕ and measurements of χ c J → ω ω and ω ϕ in ψ ( 2 S ) radiative processes

Using ( 2712 ± 14 ) × 10 6 ψ ( 2 S ) events collected with the BESIII detector at the BEPCII collider, we search for the decays η c ( 2 S ) → ω ω and η c ( 2 S ) → ω ϕ via the process ψ ( 2 S ) → γ η c ( 2 S ) . No statistically significant signals are observed. The upper limits of their product branching fractions at the 90% confidence level are determined to be B ( ψ ( 2 S ) → γ η c ( 2 S ) , η c ( 2 S ) → ω ω ) < 1.04 × 10 − 6 and B ( ψ ( 2 S ) → γ η c ( 2 S ) , η c ( 2 S ) → ω ϕ ) < 1.85 × 10 − 7 , respectively. We also update the branching fractions of χ c J → ω ω and χ c J → ω ϕ via the ψ ( 2 S ) → γ χ c J transition. Their branching fractions are determined to be B ( χ c 0 → ω ω ) = ( 10.66 ± 0.11 ± 0.57 ) × 10 − 4 , B ( χ c 1 → ω ω ) = ( 6.43 ± 0.07 ± 0.31 ) × 10 − 4 , B ( χ c 2 → ω ω ) = ( 8.75 ± 0.08 ± 0.42 ) × 10 − 4 , B ( χ c 0 → ω ϕ ) = ( 1.18 ± 0.03 ± 0.07 ) × 10 − 4 , B ( χ c 1 → ω ϕ ) = ( 2.04 ± 0.15 ± 0.11 ) × 10 − 5 , and B ( χ c 2 → ω ϕ ) = ( 9.58 ± 1.07 ± 0.76 ) × 10 − 6 , where the first uncertainties are statistical and the second are systematic. Published by the American Physical Society 2025

Ablikim, M.↗
DOE OSTI2025

Observation of the W -Annihilation Process D s + → ω ρ + and Measurement of D s + → ϕ ρ + in D s + → π + π + π − π 0 π 0 Decays

We present the first amplitude analysis and branching fraction measurement of the decay D s + → π + π + π − π 0 π 0 , using e + e − collision data collected with the BESIII detector at center-of-mass energies between 4.128 and 4.226 GeV corresponding to an integrated luminosity of 7.33 fb − 1 , and report the first observation of the pure W -annihilation decay D s + → ω ρ + with a branching fraction of ( 0.99 ± 0.0 8 stat − 0.07 + 0.05 syst ) % . In comparison to the low significance of the D wave in the decay D s + → ϕ ρ + , the dominance of the D wave over the S and P waves, with a fraction of ( 51.85 ± 7.2 8 stat − 7.90 + 4.83 syst ) % observed in the decay D s + → ω ρ + , provides crucial information for the “polarization puzzle,” as well as for the understanding of charm meson decays. The branching fraction of D s + → π + π + π − π 0 π 0 is measured to be ( 4.41 ± 0.1 5 stat ± 0.1 3 syst ) % . Moreover, the branching fraction of D s + → ϕ ρ + is measured to be ( 3.98 ± 0.3 3 stat − 0.19 + 0.21 syst ) % , and the R ϕ = B ( ϕ → π + π − π 0 ) / B ( ϕ → K + K − ) is determined to be ( 0.222 ± 0.01 9 stat − 0.016 + 0.016 syst ), which is consistent with the previous measurement based on charm meson decays, but deviates from the results from e + e − annihilation and K − N scattering experiments by more than 3 σ . Published by the American Physical Society 2025

Ablikim, M.↗
DOE OSTI2022

BACCHUS Analysis of Weak Lines in APOGEE Spectra (BAWLAS)

Elements with weak and blended spectral features in stellar spectra are challenging to measure and require specialized analysis methods to precisely measure their chemical abundances. In this work, we have created a catalog of approximately 120,000 giants with high signal-to-noise Apache Point Observatory Galactic Evolution Experiment (APOGEE) Data Release 17 (DR17) spectra, for which we explore weak and blended species to measure Na, P, S, V, Cu, Ce, and Nd abundances and 12 C/ 13 C isotopic ratios. We employ an updated version of the Brussels Automatic Code for Characterizing High-accuracy Spectra (BACCHUS) code to derive these abundances using the stellar parameters measured by APOGEE's DR17 Stellar Parameters and Chemical Abundances Pipeline, quality flagging to identify suspect spectral lines, and a prescription for upper limits. Combined, these allow us to provide our BACCHUS Analysis of Weak Lines in APOGEE Spectra catalog of precise chemical abundances for these weak and blended species, which agrees well with the literature and improves upon APOGEE abundances for these elements, some of which are unable to be measured with APOGEE's current, grid-based approach without computationally expensive expansions. This new catalog can be used alongside APOGEE and provides measurements for many scientific applications ranging from nuclear physics to Galactic chemical evolution and Milky Way population studies. To illustrate this we show some examples of uses for this catalog, such as showing that we observe stars with enhanced s-process abundances or that we can use the 12 C/ 13 C ratios to explore extra mixing along the red giant branch.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2025

Energy Scheduling-based Operating Envelopes including a Distribution System Branch Screening Algorithm

This paper presents an energy scheduling-based formulation for computing operating envelopes including a distribution branch screening algorithm, termed DBS-ES. The contribution of the paper is two-fold: firstly, it presents an innovative methodology for calculating operating envelopes using energy scheduling (baseline), and secondly, it enhances this methodology by incorporating a custom distribution branch screening algorithm (DBS-ES). The custom algorithm leverages power system knowledge to reduce both model build time and total processing time while maintaining the same scheduling results as the baseline. The effectiveness of the proposed approach is demonstrated through experiments on the IEEE13, IEEE123, and EPRI Secondary test feeders. Results highlight a 24.5% decrease in model build time and an 8.17% decrease in total processing time when using DBS-ES compared to the baseline, specifically for the IEEE123 test feeder. Additionally, the paper briefly discusses the influence of utility-controlled storage on computing operating envelopes, noting a general incre

24 POWER TRANSMISSION AND DISTRIBUTION↗
DOE OSTI2026

Hydrogenolysis Versus Hydrocracking for Polyolefin Upcycling

Global plastic production has reached 413.8 million metric tons in 2024 and is forecasted to surpass 1.2 billion metric tons by 2050. Polyolefins, mainly polyethylene (PE) and polypropylene (PP), dominate single-use packaging and account for approximately 55% of global plastic waste. The chemical inertness that makes these materials desirable for commercial applications also renders them persistent in the environment. Current recycling technologies have proven to be insufficient to divert plastic waste from landfills or environmental loss due to technical limitations and poor economic incentives. Conventional mechanical recycling is a form of downcycling, in which the polymer remelting process results in products with inferior material properties and reduced market value. Pyrolysis, a thermochemical route used for the chemical recycling of plastic wastes into refinery feedstock, requires severe conditions, typically 400–600 °C in an oxygen-free environment. The high temperature drives up energy costs and produces a wide range of poorly defined products, including undesirable light gases and heavy tars that pose challenges for downstream processing. As an alternative, catalytic chemical recycling offers a promising route for converting waste polyolefins back into value-added hydrocarbons—such as fuels, lubricant base oils, and other chemical feedstocks—at temperatures typically below 300 °C. This opinion article focuses on two dominant pathways in heterogeneous catalysis that are used to cleave the C–C bonds of polyolefins: hydrogenolysis and hydrocracking. Both catalytic pathways have the potential to selectively convert polyolefin waste into valuable fuels and chemical feedstocks under mild conditions. Notably, while hydrocracking primarily yields branched hydrocarbon products, hydrogenolysis predominantly produces linear hydrocarbons. Here, we compare the mechanisms and catalyst designs for hydrocracking and hydrogenolysis, analyze critical technical challenges from catalyst stability to process engineering, and provide an outlook on how these complementary pathways can be used to repurpose plastic waste into valuable products.

Zhang, Ruoxi [Iowa State Univ., Ames, IA (United S↗
DOE OSTI2025

Internally Catalyzed Hydrogen Atom Transfer (I-CHAT)—A New Class of Reactions in Combustion Chemistry

The current paradigm of low-T combustion and autoignition of hydrocarbons is based on the sequential two-step oxygenation of fuel radicals. The key chain-branching occurs when the second oxygenation adduct (OOQOOH) is isomerized releasing an OH radical and a key ketohydroperoxide (KHP) intermediate. The subsequent homolytic dissociation of relatively weak O–O bonds in KHP generates two more radicals in the oxidation chain leading to ignition. Based on the recently introduced intramolecular “catalytic hydrogen atom transfer” mechanism (J. Phys. Chem. 2024, 128, 2169), abbreviated here as I-CHAT, we have identified a novel unimolecular decomposition channel for KHPs to form their classical isomers—enol hydroperoxides (EHP). The uncertainty in the contribution of enols is typically due to the high computed barriers for conventional (“direct”) keto–enol tautomerization. Remarkably, the I-CHAT dramatically reduces such barriers. The novel mechanism can be regarded as an intramolecular version of the intermolecular relay transfer of H-atoms mediated by an external molecule following the general classification of such processes (Catal. Rev.-Sci. Eng. 2014, 56, 403). Here, we present a detailed mechanistic and kinetic analysis of the I-CHAT-facilitated pathways applied to n-hexane, n-heptane, and n-pentane models as prototype molecules for gasoline, diesel, and hybrid rocket fuels. We particularly examined the formation kinetics and subsequent dissociation of the γ-enol-hydroperoxide isomer of the most abundant pentane-derived isomer γ-C5-KHP observed experimentally. To gain molecular-level insight into the I-CHAT catalysis, we have also explored the role of the internal catalyst moieties using truncated models. All applied models demonstrated a significant reduction in the isomerization barriers, primarily due to the decreased ring strain in transition states. In addition, the longer-range and sequential H-migration processes were also identified and illustrated via a combined double keto–enol conversion of heptane-2,6-diketo-4-hydroperoxide as a potential chain-branching model. To assess the possible impact of the I-CHAT channels on global fuel combustion characteristics, we performed a detailed kinetic analysis of the isomerization and decomposition of γ-C5-KHP comparing I-CHAT with key alternative reactions—direct dissociation and Korcek channels. Calculated rate parameters were implemented into a modified version of the n-pentane kinetic model developed earlier using RMG automated model generation tools (ACS Omega, 2023, 8, 4908). Simulations of ignition delay times revealed the significant effect of the new pathways, suggesting an important role of the I-CHAT pathways in the low-T combustion of large alkanes.

Biochemistry & Molecular Biology↗
DOE OSTI2024

Bioblendstocks to Optimize Mixing Controlled Compression Ignition (MCCI) Engines

In this project, a team of researchers from the University of Massachusetts Lowell, the University of Maine, and Mainstream Engineering developed an integrated process for the product of bioblendstocks to optimize mixing controlled compression ignition (MCCI) engines. The objective was to improve the energy density, sooting propensity, and cetane number of base diesel fuel while maintaining cold weather behavior. The process converts woody biomass (e.g. sawmill residues) into bio-oil through selective fast pyrolysis; the bio-oil is then selectively upgraded to form selectively oxygenated, minimally-branched hydrocarbons using non-noble metal catalysts in combination with metal-catalyzed hydrogenation. Advanced predictive models, in conjunction with existing property databases, and experimental testing are used to evaluate overall bioblendstock properties and their impact on base diesel fuel. An iterative, targeted upgrading approach was implemented to optimize the proposed bioblendstock’s properties. Assessment methodologies included techno-economic analysis, life-cycle assessment, property testing, and engine testing. Ultimately, the project team successfully produced a viable bioblendstock while identifying critical process points related to scale-up efforts. It was found that producing pyrolysis oils at 500 degrees C and with pine particle sizes of 1-2 mm led to bio-oil with a higher yield (of approximately 45 wt%) and rich amounts of aromatic alcohols. The resultant pyrolysis oil was then upgraded using a sequence of mild hydrotreating, followed by catalytic etherification and esterification, followed by another final mild hydrotreating to produce a blendstock containing saturated species with a limited, but non-zero, amount of oxygen. The aromatic alcohols produced by pyrolysis were especially helpful in this regard, as the resulting bicycloethers and derivatives exhibited high cetane numbers. While most bulk properties of the bioblendstock met or exceeded targeted thresholds, viscosity and cloud point notably fell outside the expected range; this could be addressed by blending limits and/or through the use of additives that are commonplace in current refinding practices. Identification of a bioblendstock that can be produced economically at scale while improving the performance and emissions characteristics of internal combustion engines positively affects the economy by boosting domestic fuel production and the environment by decreasing harmful emissions and increasing efficiency.

09 BIOMASS FUELS↗