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

Intrinsically Bifunctional and Tunable Tungsten Carbide Catalysts Enable Efficient PVC-Compatible Polyolefin Hydrocracking

Hydrocracking is a promising route for the chemical recycling of polyolefins (PO), converting them into short hydrocarbons over bifunctional catalysts with metal sites for hydrogenation and dehydrogenation, and Brønsted acid sites (BAS) for isomerization and C–C bond cleavage. However, PO feedstocks containing polyvinyl chloride (PVC) can release chlorine (Cl) under reaction conditions, deactivating conventional noble metal/zeolite catalysts. Moreover, the lack of site intimacy and the presence of micropores within conventional catalysts create challenges around the transport of high-molecular-weight, sterically encumbered polymer intermediates. Here, in this study, we report tungsten carbides (W x C) as a novel type of bifunctional catalysts that address these challenges. W/W 2 C phases on W x C offer “metal” sites, and −OH on WO x species introduces BAS in close proximity. The “metal”:BAS ratio can be tuned through carburization temperature, leading to a volcano-shaped activity trend reflecting the requirement for metal–BAS balance. Kinetic data demonstrate that each PO chain undergoes sequential cleavage, while trends in cracking ideality and selectivity follow those in short-alkane hydrocracking. On the per-BAS basis, W x C is more efficient than conventional bifunctional catalysts by more than an order of magnitude, due to enhanced polymer transport. They maintain or show increased activity with 10 wt % PVC in the substrate. This work establishes transition-metal carbides as earth-abundant bifunctional catalysts with unique site proximity and heteroatom compatibility. These features, along with the broad structure space for rational tuning, make them promising options to tackle specific challenges that polymer feedstocks present in hydrocracking.

Nwachukwu, Uchenna C. [Univ. of Akron, OH (United ↗
DOE OSTI2026

Cyclodextrin-Derived Porous Liquids Enabled by In Situ Solvation Shell Formation

Porous liquids (PLs) represent a unique platform for molecular separations by combining permanent porosity with liquid-phase mobility. However, it remains a formidable challenge to construct and stabilize PLs with sub-5 Å pores using readily available porous host and liquid media. Here, we report the construction of cyclodextrin (CD)-derived PLs enabled by in situ solvation shell formation. The acid–base neutralization reaction between CD and an organic base was leveraged to generate a thin ionic solvation shell around the CD host, effectively liquefying CD and preventing its segregation in the liquid base medium while preserving accessible molecular-scale cavities. Spectroscopic analysis, neutron scattering, density functional theory calculations, and molecular dynamics simulations collectively confirm the structural evolution and existence of abundant internal porosity in PLs. The unique architectures of CD-derived PLs enable highly selective encapsulation of fluorinated alkanes and significantly enhanced uptake of inert gases. This facile and generalizable strategy enables construction of high-quality PLs with engineered ultramicroporosity to facilitate molecular separations.

Cavities↗
DOE OSTI2026

Low-Temperature Non-Oxidative Coupling of Methane on Atomically Dispersed Titanium–Aluminum–Boron Nanopowder

Nonoxidative coupling of methane represents a long-standing challenge in heterogeneous catalysis, as it requires activation of the carbon–hydrogen (C–H) bond, controlled carbon–carbon (C–C) bond formation, and effective hydrogen management without relying on oxidants. Here, we report a low-temperature C–H activation and nonoxidative C–C coupling of methane over atomically dispersed titanium–aluminum–boron nanopowder (Ti–Al–B NP) utilizing a catalytic microreactor coupled to synchrotron single-photon photoionization reflectron time-of-flight mass spectrometry. The soft-ionization, in situ probing method detects the nascent reaction products and radical intermediates under operando conditions, including methyl radical, C2 hydrocarbons, and molecular hydrogen. Methane activation is initiated at 800 K, approximately 700 K below the gas-phase decomposition threshold, leading predominantly to ethylene formation with selectivity reaching up to 78% among the C–C coupled products. Electronic structure calculations on model Ti–Al–B clusters elucidate a cooperative catalytic mechanism in which titanium enables methane adsorption and C–H activation, boron acts as a reversible hydrogen reservoir, and aluminum stabilizes methylene intermediates, thereby facilitating selective C–C coupling and dehydrogenation. These findings establish a distinct catalyst architecture for nonoxidative methane coupling based on earth abundant elements alternative to expensive platinum and other noble metal-containing conventional catalysts and provide molecular-level design principles for controlling dehydrogenation and subsequent C–C bond formation in challenging light alkane conversions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Isopentane Disproportionation in Lewis Acidic Chloroaluminate Ionic Liquid

Lewis acidic chloroaluminate ionic liquid diluted in dichloromethane catalyzes the disproportionation of alkanes, such as isopentane, via carbenium ions in a reaction readily initiated by carbenium ion precursors such as tert-butyl chloride (TBC). The carbenium ion-AlCl 4 – ion-pairs stabilized by the ionic liquid-dichloromethane solution are the key intermediates in two distinctive kinetic regimes, i.e., a transient regime (0–5 min) and a steady-state regime (after 5 min). The transient regime constitutes the majority of isopentane conversion and is governed by the initial carbenium ion concentration. In the steady-state regime, disproportionation occurs at a considerably lower rate, affected by the carbenium ion concentration, the concentration of the ionic liquid, and the reaction temperature. The formation of alkenes observed in the 1 H NMR spectra of the reacting substrates, along with the DFT calculations, suggests that deprotonation of carbenium ion-pairs reduces their concentration, decreasing, in turn, the reaction rate. Kinetic modeling indicates that the transient regime is significantly controlled by the hydride transfer (k HT ) and the deprotonation rate constants (k DP ), while the steady-state regime is additionally influenced by the alkene protonation rate constant (k –DP ). The overall activation energy of the reaction at the steady state, expressed as E a,steady-state regime = E a,HT – E a,DP + E a,–DP , was 54 kJ/mol. The reaction mechanism and the kinetics highlight the potential of Lewis acid-catalyzed conversions of hydrocarbons under remarkably mild conditions.

Deprotonation↗
DOE OSTI2024

Light-driven C–H activation mediated by 2D transition metal dichalcogenides

C–H bond activation enables the facile synthesis of new chemicals. While C–H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C–H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C–C coupling mediated by 2D TMDCs to promote C–H activation and carbon dots synthesis. Our results shed light on 2D materials for C–H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Carbon-negative hydrogen: aqueous phase reforming (APR) of glycerol over NiPt bimetallic catalyst coupled with CO 2 sequestration

Herein we report the production of high-pressure (19.3 bar), carbon-negative hydrogen (H 2 ) from glycerol with a purity of 98.2 mol% H 2 , 1.8 mol% light hydrocarbons (mainly methane), and 400 ppm of CO. Aqueous phase reforming (APR) of 10 wt% glycerol solution was studied with a series of NiPt alumina bimetallic catalysts supported on alumina. The Ni 8 Pt 1 -450 catalyst had the highest hydrogen selectivity (95.6%) and the lowest alkanes selectivity (3.7%) of the tested catalysts. The hydrogen selectivity decreased in the order of Ni 8 Pt 1 -450 > Ni 8 Pt 1 -260 > Ni 1 Pt 1 -260 > Pt-260. The CO 2 was sequestered with CaO adsorbent which formed CaCO 3 . We measured the adsorption capacity of the CaO adsorbent at different temperatures. Life cycle analysis showed that the APR of glycerol coupled with CO 2 capture has net negative CO 2 equivalent greenhouse gas emissions. The CO 2 emissions are –9.9 kg CO 2 eq./kg H 2 and –50.1 kg CO 2 eq./kg H 2 when grid electricity and renewable electricity are used, respectively, and the CO 2 is allocated respectively to the mass of products produced. The cost of this H 2 (denoted as “green-emerald”) was estimated to be 2.4 USD per kg H 2 when grid electricity is used and 2.7 USD per kg H 2 when using renewable electricity. The cost of glycerol has the highest contribution of 1.71 USD per kg H 2 . As a result, participation in the carbon credit markets can further decrease the price of the produced H 2 .

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

Stabilization of reactive rare earth alkyl complexes through mechanistic studies

Rare earth tris(alkyl) complexes such as M(CH 2 SiMe 3 ) 3 (sol) n are widely used as precursors for many compounds and as homogeneous catalysts for alkene polymerization and alkane functionalization. However, the thermal instability of those most conveniently made from the commercially available lithium salt of the neosilyl anion, LiCH 2 SiMe 3 , Li(r), restricts their utility. We present a new range of synthetically useful, more kinetically stable rare earth neosilyl solvates, derived from a full kinetic study of the various possible decomposition mechanisms of 7 known and 12 new solvated rare earth neosilyl complexes M(CH 2 SiMe 3 ) 3 (sol) n M = Sc(III), Y(III), Lu(III), Sm(III), and sol = THF; TMEDA; DMPE; diglyme ((CH 3 ) 2 (OCH 2 CH 2 ) 2 O, G 2 ), triglyme ((CH 3 ) 2 (OCH 2 CH 2 ) 3 O, G 3 ). Surprisingly, simply using higher-denticity donors to sterically disfavor neosilyl γ-H elimination is not effective. While Sc(r) 3 ((CH 3 ) 2 (OCH 2 CH 2 ) 2 O) has a half-life, t 1/2 , of 258.1 h, six times longer than for Sc(r) 3 (C 4 H 8 O) 2 (t 1/2 = 43 h), Lu(r) 3 ((CH 3 ) 2 (OCH 2 CH 2 ) 2 O) and Y(r) 3 ((CH 3 ) 2 (OCH 2 CH 2 ) 2 O) do not show the expected, analogous increased t 1/2 . This is because new decomposition pathways appear for poorly fitting donors. Finally, kinetic studies demonstrate the impact of small, and increasing amounts of LiCl on the kinetics of the reactivity of the smaller alkyls Y(r) 3 (THF) 2 and Lu(r) 3 (THF) 2 ; molecules used in hydrocarbon chemistry and catalysis for fifty years. A new route to pure Y(r) 3 (THF) 2 , which avoids the traditional use of Li(r), is presented.

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

Computational insights into hydrogen adsorption energies on medium-entropy oxides

High entropy oxides (HEOs) have emerged as promising catalysts for several important chemical transformations including alkane activation. Hydrogen adsorption energy (HAE) has been used as a key descriptor for many reactions including methane C–H activation and hydrogen evolution reactions. Hence, understanding the relationship between HAEs and the surface chemistry of HEO surfaces could lay the foundation for meaningful correlations among methane C–H activation, HAE, and the complex, local environment of HEO surfaces. Here, we used a medium-entropy oxide as a prototypical system – Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 O with a rock-salt structure – to interrogate these relationships. We sampled 2000 different surfaces of its (100) plane and calculated the HAEs at randomly chosen surface O sites using density functional theory (DFT). Our analysis of the 2000 data points reveals that the HAEs at the surface O sites are significantly influenced by the local environment around the adsorption sites, particularly the nature of the metal atom directly below the surface O site where H adsorbs. After comparing several popular graph-neural-network-based machine learning models, we found that the DimeNet++ model performed best achieving satisfactory accuracy in predicting HAEs for both Mg 0.25 Ni 0.25 Cu 0.25 Zn 0.25 O and slightly varied compositions. Our work underscores the promise of such models and the need for further refinement to address the complexity of HEOs.

Song, Haohong [Vanderbilt Univ., Nashville, TN (Un↗
DOE OSTI2026

From molecular to macroscopic: predicting liquid–liquid phase equilibria and small-angle scattering of mixtures of organic liquids from atomistic simulation using Kirkwood–Buff theory

Macroscopic phase equilibria between solutions define the functionality of many biological and industrial processes, yet they are challenging to predict due to the inherent complexity of liquids containing large molecules. This work introduces an approach for the purely predictive calculation of such phase equilibria in temperature-composition space from molecular dynamics (MD) simulations at one temperature in the single-phase region. We use an approach developed previously to obtain the entropic and enthalpic contributions to the free energy of mixing from the atomic-scale information given by MD simulations via Kirkwood–Buff theory. This allows us to accurately estimate the free energy of mixing as a function of temperature, and thus obtain liquid–liquid phase equilibria, including liquid–liquid critical points, associated binodal and spinodal lines, and composition fluctuations across a region of temperature and composition. Results for binary malonamide–alkane systems are validated by comparison to a direct experimental probe of the fluctuations: the small angle X-ray scattering intensity near zero wavenumber. The MDKB → Phase method demonstrated here provides a significant improvement in predicting liquid–liquid equilibria and free energy as a function of temperature for our systems of interest compared to conventional thermodynamic models. The accurate performance of this purely predictive approach lies in its preservation of atomistic details when determining thermodynamic properties. Furthermore, its inherent extensibility to multi-component systems will likely make the MDKB → Phase approach a valuable general tool for connecting molecular interactions to macroscopic phase equilibria and for the computational screening of materials for targeted thermodynamic behavior.

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

Linear-scaling quadruple excitations in local pair natural orbital coupled-cluster theory

Here, we present a fast, asymptotically linear-scaling implementation of the perturbative quadruples energy correction in coupled-cluster theory using local natural orbitals. Our work follows the domain-based local pair natural orbital (DLPNO) approach previously applied to lower levels of excitations in coupled-cluster theory. Our DLPNO-CCSDT(Q) algorithm uses converged doubles and triples amplitudes from a preceding DLPNO-CCSDT computation to compute the quadruples amplitude and energy in the quadruples natural orbital (QNO) basis. We demonstrate the compactness of the QNO space, showing that more than 95% of the (Q) correction can be recovered using relatively loose natural orbital cutoffs, compared to the tighter cutoffs used in pair and triples natural orbitals at lower levels of coupled-cluster theory. We also highlight the accuracy of our algorithm in the computation of relative energies, which yields deviations of sub-kJ mol −1 in relative energy compared to the canonical CCSDT(Q). Timings are conducted on a series of growing linear alkanes (up to 10 carbons and 608 basis functions) and water clusters (up to 49 water molecules and 2842 basis functions) to establish the asymptotic linear-scaling of our DLPNO-(Q) algorithm.

Auxiliary functions↗
DOE OSTI2024

Demystifying group-4 polyolefin hydrogenolysis catalysis: Gaseous propane hydrogenolysis mechanism over the same catalysts

A kinetic/mechanistic investigation of gaseous propane hydrogenolysis over the single-site heterogeneous polyolefin depolymerization catalysts AlS/ZrNp 2 and AlS/HfNp 2 (AlS = sulfated alumina, Np = neopentyl), is use to probe intrinsic catalyst properties without the complexities introduced by time- and viscosity-dependent polymer medium effects. In a polymer-free automated plug-flow catalytic reactor, propane hydrogenolysis turnover frequencies approach 3,000 h −1 at 150 °C. Both catalysts exhibit approximately linear relationships between rate and [H 2 ] at substoichiometric [H 2 ] with rate law orders of 0.66 ± 0.09 and 0.48 ± 0.07 for Hf and Zr, respectively; at higher [H 2 ], the rates approach zero-order in [H 2 ]. Reaction orders in [C 3 H 8 ] and [catalyst] are essentially zero-order under all conditions, with the former implying rapid, irreversible alkane binding/activation. This rate law, activation parameter, and DFT energy span analysis support a scenario in which [H 2 ] is pivotal in one of two plausible and competing rate-determining transition states—bimolecular metal-alkyl bond hydrogenolysis vs. unimolecular β-alkyl elimination. The Zr and Hf catalyst activation parameters, ΔH ‡ = 16.8 ± 0.2 kcal mol −1 and 18.2 ± 0.6 kcal mol −1 , respectively, track the relative turnover frequencies, while ΔS ‡ = −19.1 ± 0.8 and −16.7 ± 1.4 cal mol −1 K −1 , respectively, imply highly organized transition states. These catalysts maintain activity up to 200 °C, while time-on-stream data indicate multiday activities with an extrapolated turnover number ~92,000 at 150 °C for the Zr catalyst. This methodology is attractive for depolymerization catalyst discovery and process optimization.

03 NATURAL GAS↗
DOE OSTI2024

Source apportionment of airborne volatile organic compounds near unconventional oil and gas development

Oil and natural gas (ONG) extraction emits volatile organic compounds (VOCs). Certain VOCs are identified as hazardous air pollutants (HAPS) while others contribute to ozone formation. This study examines the impact of ONG operations on VOC levels during the development of multi-well ONG pads in suburban Broomfield, Colorado. From October 2018 to December 2020, weekly VOC measurements were taken at 18 sites across the area. These included spots near well pads, in adjacent neighborhoods, and at a background site, covering various stages of well pad development including drilling, hydraulic fracturing, flowback, and production. Analysis using Positive Matrix Factorization (PMF) identified six factors, including combustion, background/biogenic sources, light and complex alkanes, drilling activities, and ONG acetylene. Factors linked to local ONG activities exhibited clear temporal and spatial correlations with Broomfield well development. Benzene source analysis revealed distinct contribution gradients, with ONG-related sources notably influencing areas near the well pads, particularly in pre-production. ONG-related weekly benzene contributions varied from 9% to 63% at a community background site and 18% to 89% in a neighborhood close to a well pad.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Removal of trace gases can both increase and decrease cloud droplet formation

Aerosols consist of liquid or solid particles dispersed in a gas. Aerosol measurements generally rely on drying the particles before quantifying their physicochemical properties. This drying can potentially remove semivolatile compounds from the particles. Here, we show size-resolved cloud condensation nuclei (CCN) measurements quantifying the hygroscopicity parameter in the presence and absence of a denuder. The denuder efficiently removed alkanes and weakly functionalized acids, aldehydes, and alcohols with fewer than 10 carbon atoms from the gas phase. Denuding organic compounds perturbed the CCN-derived hygroscopicity parameter by up to 50%. Denuding either rendered the particles more or less CCN active, and the direction of the effect depended on sample relative humidity and trace gas concentration. The effect was weakest in early spring and strongest in late spring and summer. The measurements demonstrate an unexpectedly strong coupling between the particle and gas phase, influencing CCN activity through either volatilization or surface adsorption, or both.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Cultivation of novel Atribacterota from oil well provides new insight into their diversity, ecology, and evolution in anoxic, carbon-rich environments

Background: The Atribacterota are widely distributed in the subsurface biosphere. Recently, the first Atribacterota isolate was described and the number of Atribacterota genome sequences retrieved from environmental samples has increased significantly; however, their diversity, physiology, ecology, and evolution remain poorly understood. Results: We report the isolation of the second member of Atribacterota, Thermatribacter velox gen. nov., sp. nov., within a new family Thermatribacteraceae fam. nov., and the short-term laboratory cultivation of a member of the JS1 lineage, Phoenicimicrobium oleiphilum HX-OS.bin.34 TS , both from a terrestrial oil reservoir. Physiological and metatranscriptomics analyses showed that Thermatribacter velox B11 T and Phoenicimicrobium oleiphilum HX-OS.bin.34 TS ferment sugars and n-alkanes, respectively, producing H 2 , CO 2 , and acetate as common products. Comparative genomics showed that all members of the Atribacterota lack a complete Wood-Ljungdahl Pathway (WLP), but that the Reductive Glycine Pathway (RGP) is widespread, indicating that the RGP, rather than WLP, is a central hub in Atribacterota metabolism. Ancestral character state reconstructions and phylogenetic analyses showed that key genes encoding the RGP (fdhA, fhs, folD, glyA, gcvT, gcvPAB, pdhD) and other central functions were gained independently in the two classes, Atribacteria (OP9) and Phoenicimicrobiia (JS1), after which they were inherited vertically; these genes included fumarate-adding enzymes (faeA; Phoenicimicrobiia only), the CODH/ACS complex (acsABCDE), and diverse hydrogenases (NiFe group 3b, 4b and FeFe group A3, C). Finally, we present genome-resolved community metabolic models showing the central roles of Atribacteria (OP9) and Phoenicimicrobiia (JS1) in acetate- and hydrocarbon-rich environments. Conclusion: Our findings expand the knowledge of the diversity, physiology, ecology, and evolution of the phylum Atribacterota. This study is a starting point for promoting more incisive studies of their syntrophic biology and may guide the rational design of strategies to cultivate them in the laboratory.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Data for Carbon-negative Hydrogen: Aqueous Phase Reforming (APR) of Glycerol over NiPt Bimetallic Catalyst Coupled with CO2 Sequestration

Herein we report the production of high-pressure (19.3 bar), carbon-negative hydrogen (H2) from glycerol with a purity of 98.2 mol% H2, 1.8 mol% light hydrocarbons (mainly methane), and 400 ppm of CO. Aqueous phase reforming (APR) of 10 wt% glycerol solution was studied with a series of NiPt alumina bimetallic catalysts supported on alumina. The Ni8Pt1-450 catalyst had the highest hydrogen selectivity (95.6%) and the lowest alkanes selectivity (3.7%) of the tested catalysts. The hydrogen selectivity decreased in the order of Ni8Pt1-450 > Ni8Pt1-260 > Ni1Pt1-260 > Pt-260. The CO2 was sequestered with CaO adsorbent which formed CaCO3. We measured the adsorption capacity of the CaO adsorbent at different temperatures. Life cycle analysis showed that the APR of glycerol coupled with CO2 capture has net negative CO2 equivalent greenhouse gas emissions. The CO2 emissions are −9.9 kg CO2 eq./kg H2 and −50.1 kg CO2 eq./kg H2 when grid electricity and renewable electricity are used, respectively, and the CO2 is allocated respectively to the mass of products produced. The cost of this H2 (denoted as “green-emerald”) was estimated to be 2.4 USD per kg H2 when grid electricity is used and 2.7 USD per kg H2 when using renewable electricity. The cost of glycerol has the highest contribution of 1.71 USD per kg H2. Participation in the carbon credit markets can further decrease the price of the produced H2.

Catalysis↗
DOE OSTI2024

Novel Microbial Routes to Synthesize Industrially Significant Precursor Compounds

Ethylene is the most widely employed organic precursor compound in industry. The potential to impact ethylene formation via recently discovered microbial processes is tenable using plentiful CO2 feedstocks. The overall long-term objective of this project was to develop an industrially compatible microbial process to synthesize ethylene in high yields. The key objective of this project was to fully define and initially characterized a recently discovered and genetically regulated anaerobic pathway to produce high levels of ethylene called the Dihydroxyacetone Phosphate - Ethylene Pathway in phototrophic bacteria. This was addressed through the following specific aims: 1. Fully probe the catalytic potential of all enzymes of the DHAP ethylene pathway and determine the regulatory mechanism of DHAP-ethylene pathway gene expression. 2. Discover effective and active ethylene enzymes encoded in cultured and uncultured organisms from anoxic environments. 3.Model the thermodynamics and kinetics of ethylene synthetic pathways to guide engineering efforts in integrating best performing DHAP-ethylene pathway enzymes into model bacteria chassis for enhance ethylene yields. Through this project we discovered the initially missing genetic and enzyme component of the DHAP-ethylene pathway that directly synthesized ethylene and other important industrial compounds like methane and ethane from specific substrates. We uncovered and partially characterized a nitrogenase-like reductase that functions in DHAP-ethylene pathway specifically and in methionine synthesis in general. This nitrogenase-like system is called the Methylthio-Alkane Reductase (MAR) for its ability to cleave volatile organic sulfur compounds into methanethiol (CH3-SH) for methionine synthesis and a hydrocarbon byproduct. Key to the DHAP-ethylene pathway, MAR is the essential enzyme that cleaves 2-methylthioethanol (CH3-S-CH2-CH2-OH) into ethylene. Coordinately, we uncovered that the MAR genes and genes associated with conversion of methanethiol (CH3-SH) to methionine are under genetic control of a LysR Type Transcriptional Regulator called SalR, whose activity is dependent upon the amount of sulfate available to the cell. When sulfate as the preferred sulfur source for cell growth drops below 200 micromolar, SalR become active for expressing the MAR and methionine biosynthesis genes to enable the cell to grow from volatile organic sulfur compounds and make ethylene. Metabolic thermos-kinetic modeling revealed that these MAR reactions for ethylene and other hydrocarbon production are highly thermodynamically favorable and are one of the largest driving forces for ethylene production by the DHAP-ethylene pathway for high ethylene yields. Modeling also indicated that a key aldolase and to a lesser extent an isomerase of the DHAP-ethylene pathway for production of the ethylene precursor, 2-methylthioethanol, also would increase ethylene yields. Through metagenomic mining and gene synthesis by the JGI DNA synthesis program, over 500 aldolase and isomerase homologs were synthesized and screened. From this, variants were uncovered with substantially higher activity that increased ethylene yields 5-fold via the aldolase reaction and 1.5-fold via the isomerase reaction. Each of these elements that increase ethylene production were integrated together via plasmid under appropriate gene promoter elements in the phototrophic bacterium, Rhodospirillum rubrum, resulting in at least 3 orders of magnitude increase in ethylene yield from carbon dioxide feedstock.

10 SYNTHETIC FUELS↗
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↗