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Methanol mixing−controlled compression ignition enabled via homogeneous charge compression ignition of dimethyl ether through catalytic decomposition of methanol

Methanol is a potentially attractive fuel for marine and off−road engines owing to its availability at bunkering and global distribution locations. Although methanol is well−distributed worldwide, its fuel chemistry and ignition properties make it poorly suited as a direct drop−in replacement for diesel fuel in compression−ignition engines. However, industrial processes are regularly used to convert methanol, via catalytic dehydration, to dimethyl ether (DME) over nonprecious metal catalysts. This chemical conversion can occur at relatively low pressures, temperatures, and catalyst space velocities, highlighting a potential opportunity to generate DME via onboard catalytic dehydration of methanol. DME’s fuel kinetic and ignition properties for compression ignition are much more favorable than those of methanol or even diesel fuel, but DME is more challenging than diesel fuel or methanol to pump, store, and deliver through conventional diesel fueling injection hardware. Thus, a potential opportunity exists to use the ignition and kinetic properties of DME, with the transportation and delivery advantages of methanol, in a methanol−fueled mixing−controlled compression−ignition engine. The present work explores performance, combustion behavior, and emissions reduction opportunities for methanol mixing−controlled combustion, enabled by a HCCI of DME that represents a small fraction of the total fuel energy that can be generated onboard via catalytic dehydration of methanol.

Splitter, Derek [ORNL] (ORCID:0000000174044047)

Nuclear Reactor Heat Extraction for Synthetic Fuel Plants

This report looks at the viability and best approach when producing synthetic fuels using heat and power supplied by advanced nuclear energy systems. The report looks at a low temperature integration pathway with four types of advanced reactors: a pressurized water reactor (PWR), an advanced light water reactor (A-LWR), a sodium fast reactor (SFR), and a high-temperature gas-cooled reactor (HTGR). A failure modes and effects analysis (FMEA) of the coupling system between the nuclear plant and the synthetic fuel systems is performed with the goal of identifying the reliability of such a thermal delivery system. Furthermore, a high temperature pathway is investigated for synfuel coupling to determine if this is more efficient and more cost effective as a coupling approach.

10 - SYNTHETIC FUELS

Investigating the Combustion Performance of Dual Fuel Combustion with Diesel and Port Injected Hydrogen in a Large Bore Locomotive Engine

The heavy-duty transportation sector has primarily relied on conventional diesel combustion engines given their reliability and high thermal efficiency relative to spark ignition engines, but increased focus on reducing greenhouse gas emissions has led to investigation into alternative fuels. Gaseous hydrogen fuel has garnered a great deal of recent interest in the engine community given it has zero carbon, but hydrogen is not available at the scale and cost that petroleum fuels are currently available, and this is a barrier to adoption for industries that are looking to decarbonize their operations. Because of the fuel flexibility provided, dual fuel technology offers a pathway for some industries to adopt hydrogen as a fuel source while maintaining sufficient flexibility in times and locations where the new fuel is not yet available. This computational study investigates dual fuel combustion in a large bore locomotive engine architecture using direct injected diesel and port injected gaseous hydrogen fuel. With an optimal port fuel injection configuration from previous work, simulations of varying substitution ratio, compression ratio, manifold air temperature, diesel injection timing, and diesel injection pressure were performed to understand their effect on combustion performance. Results indicated that both increased substitution ratio and higher intake air temperature accelerates hydrogen flame propagation and can result in high peak cylinder pressures. Additionally, diesel injection timing and injection pressure were demonstrated as effective methods for controlling dual fuel combustion heat release rates.

ODonnell, Patrick Christopher

Dual atom catalysts for rapid electrochemical reduction of CO to ethylene

Strong CO adsorption and facile CO dimerization are the key challenges in electrochemical CO2 reduction towards multi-carbon (C2+) products. We recently showed that CoPc immobilized on a single-walled carbon nanotube can selectively reduce CO2 to methanol. This is enabled through molecular strain, which dramatically improves the CO adsorption energy to CoPc, which in turn facilitates methanol formation. We now examine the extended Phthalocyanine (PcEx) dual atom catalyst (DAC), which is intrinsically strained and contains two catalyst centers, making it a candidate for reducing CO to C2+ products. Using Quantum Mechanics (QM), we screened 20 elements embedded in the PcEx, seeking catalysts with weak hydrogen binding, strong CO binding, and facile CO dimerization. We identi>ied Fe, Ru, Co, and Ir as the best performers and subsequently evaluated the entire CO to C2H4 mechanism (9 steps) using each of these elements as catalysts. In terms of limiting potential and overall exergonicity, we identi>ied CoPcEx as the best catalyst, followed by IrPcEx. We then examined the full CO to C2H4 mechanism on the bimetallic IrCoPcEx catalyst using grand canonical QM to obtain the reaction energetics as a function of applied potential. We conclude that the bimetallic IrCoPcEx is most promising for ef>iciently converting CO to ethylene.

Musgrave, Charles B.

Techno-Economic Evaluation of Electrified Vehicle Options in Drayage Fleets

The electrification of drayage fleets offers potential economic and operational benefits, but the financial viability of electrified vehicles remains sensitive to battery cost, energy price, and fleet usage patterns. While total cost of ownership (TCO) is a useful benchmark, fleet operators and investors are equally concerned with investment performance metrics such as payback period (PB) and Internal Rate of Return (IRR), which better reflect financial risks and investment return timelines. This study develops a unified techno-economic framework that jointly evaluates TCO, PB, and IRR to determine when electrified trucks become cost-effective alternatives to diesel trucks. Building on a previously developed cost modeling tool and using real-world telematics data from a Class 8 drayage fleet at the Port of Savannah, the analysis incorporates projected battery cost trajectories, electricity and diesel price trends, vehicle efficiency improvements, and multiple battery capacities. Parameter ranges reflect widely cited projections and observed drayage-duty-cycle variability. A surrogate-modeling method approximates economic performance across thousands of battery cost–electricity price combinations, enabling high-resolution identification of conditions that achieve TCO parity, acceptable PB thresholds, and target IRR levels. Additionally, the study estimates the evolving share of the fleet that can feasibly electrify over time under multiple economic metrics. This integrated framework offers a novel, data-driven approach to inform risk-aware decision-making for fleet electrification and supports investment planning under evolving cost and operational conditions.

Sun, Ruixiao [ORNL] (ORCID:0000000341768676)

A Predictive Bubble Point Pressure Model for Porous Liquid Acquisition Device Screens

This article presents a simplified model for porous screen channel liquid acquisition devices based on a maximum bubble point pressure method from Adamson and Gast (1997). To validate the model, three 304 stainless steel (325 × 2300, 450 × 2750, and 510 × 3600) mesh samples were tested in methanol, acetone, isopropyl alcohol, and water. Screen pores are estimated based on analysis from scanning electron microscopy, historical data, and current test data. Results show that the bubble point pressure is proportional to the surface tension of the fluid only when accounting for nonzero contact angles. The previous assumption that bubble point pressure scales inversely with effective pore diameter is shown to be invalid, as the second finest 450 × 2750 produced the highest bubble point of the three screens. The simplified bubble point model can be used to make predictions for any pure fluid when pore diameters are based on bubble point tests and not SEM analysis.

Liquid Acquisition Device

Bacterial Bioleaching and Biorecovery for Biomining Unconventional Rare Earth Element Feedstocks

Bacterial metabolic interactions with rare earth elements (REEs) can be harnessed for biomining unconventional feedstocks like abandoned coal-mine drainage (AMD). Pennsylvania has ~500 AMD passive remediation systems that can precipitate REE rich solids. REEs include yttrium and the lanthanide series that are used in modern energy and technology. Bacteria that metabolically interact with REEs can be used for biomining in an affordable efficient process that does not require hazardous chemical additives. Currently, the microbial metal mechanisms that contribute to REE biorelease and biorecovery are poorly understood. Our work shows acidogenic bacterial isolates (Bacillus mycoides JR07 and Bacillus pseudomycoides KB7) successfully bioleach a mixed REE solution from AMD solids by their organic acid production and biofilm formation. Further, our work shows the potential for bacterial lanthanide-dependent enzymes to recover lanthanides from a mixed REE solution; here we have bacterial isolate Methylobacterium sp. B3 that can recover soluble lanthanum. Whole genome sequencing of Methylobacterium sp. B3 predict lanthanide-dependent methanol dehydrogenase XoxF. Understanding the microbial metabolism and genes involved in the REE release and recovery is crucial to optimize the biomining of AMD solids. Our work addresses the growing need to develop novel REE mining methods from unconventional feedstocks.

biogeochemistry

The Role of Tribology in the Development of an Oil-Free Turbocharger

Gas-turbine-based aeropropulsion engines are technologically mature. Thus, as with any mature technology, revolutionary approaches will be needed to achieve the significant performance gains that will keep the U.S. propulsion manufacturers well ahead of foreign competition. One such approach is the development of oil-free turbomachinery utilizing advanced foil air bearings, seals, and solid lubricants. By eliminating oil-lubricated bearings and seals and supporting an engine rotor on an air film, significant improvements can be realized. For example, the entire oil system including pipes, lines, filters, cooler, and tanks could be removed, thereby saving considerable weight. Since air has no thermal decomposition temperature, engine systems could operate without excessive cooling. Also, since air bearings have no diameter-rpm fatigue limits (D-N limits), engines could be designed to operate at much higher speeds and higher density, which would result in a smaller aeropropulsion package. Because of recent advances in compliant foil air bearings and high temperature solid lubricants, these technologies can be applied to oil-free turbomachinery. In an effort to develop these technologies and to demonstrate a project along the path to an oil-free gas turbine engine, NASA has undertaken the development of an oil-free turbocharger for a heavy duty diesel engine. This turbomachine can reach 120000 rpm at a bearing temperature of 540 C (1000 F) and, in comparison to oil-lubricated bearings, can increase efficiency by 10 to 15 percent because of reduced friction. In addition, because there are no oil lubricants, there are no seal-leakage-induced emissions.

Christopher Dellacorte

Next-Generation Energy Technologies for Connected and Automated On-Road Vehicles (NEXTCAR) - Predictive Data-Driven Vehicle Dynamics and Powertrain Control: from ECU to the Cloud (Final Scientific/Technical Report)

This project developed and demonstrated a predictive, data-driven vehicle control system designed to improve energy efficiency and driving performance. The team created intelligent self-driving car technology that optimizes fuel and electricity use by proactively planning vehicle actions. By combining Level 4 autonomous driving capabilities with vehicle-to-everything (V2X) connectivity, the system enables vehicles to adjust speed and change lanes in response to traffic signals, surrounding vehicles, and road conditions, reducing unnecessary stops and delays. In testing, the system improved vehicle fuel economy by more than 30% and reduced travel time by approximately 10%, compared to a conventional adaptive cruise control baseline. These results demonstrate the technical effectiveness of using predictive, V2X-enabled strategies, such as traffic light timing and surrounding traffic awareness, to inform real-time vehicle powertrain control and driving behavior. Additionally, a supporting cloud platform was developed to provide dispatch and route recommendations as well as to log vehicle data, demonstrating the economic feasibility of this approach at the fleet level. By optimizing dispatching and routing operations, this technology enables electric fleet operators to use their vehicles more efficiently and reduce reliance on diesel backups, lowering both operating costs and energy consumption. Overall, this project’s technology advances the future of clean, energy-efficient transportation, enabling vehicles and fleets to reduce energy waste, cut costs, and lower emissions through intelligent automation and connectivity.

33 ADVANCED PROPULSION SYSTEMS

CH3OH and HCN in Interstellar Comet 3I/ATLAS Mapped with the ALMA Atacama Compact Array: Distinct Outgassing Behaviors and a Remarkably High CH3OH/HCN Production Rate Ratio

We report the detection of methanol (CH3OH) toward interstellar comet 3I/ATLAS using the At-acama Compact Array of the Atacama Large Millimeter/Submillimeter Array (ALMA) on UT 2025 August 28, September 18 and 22, and October 1, and of hydrogen cyanide (HCN) on September 12 and 15. These observations spanned pre-perihelion heliocentric distances (r H ) of 2.6 – 1.7 au. The molecules showed outgassing patterns distinct from one another, with HCN production being depleted in the sunward hemisphere of the coma, whereas CH3OH was enhanced in that direction. Statistical analysis of molecular scale lengths in 3I/ATLAS indicated that CH3OH included production from coma sources at Lp > 258 km at 99% confidence. However low signal-to-noise on long baselines, which sample emission on small spatial scales closest to the nucleus, prevented definitively ruling out CH3OH as purely a parent species. In contrast, HCN production was indistinguishable from direct nucleus sublimation. The CH3OH production rate increased sharply from August through October, including an uptick near the inner edge of the H2O sublimation zone at rH = 2 au. Compared to comets measured to date at radio wavelengths, the derived CH3OH/HCN ratios in 3I/ATLAS of 124+30−34 and 79+11−14on September 12 and 15, respectively, are among the most enriched values measured in any comet, surpassed only by anomalous solar system comet C/2016 R2 (PanSTARRS)

Comae

Analysis of Gas Absorption to A Thin Liquid Film in the Presence of A Zero-Order Chemical Reaction

The paper presents a detailed theoretical analysis of the process of gas absorption to a thin liquid film adjacent to a horizontal rotating disk. The film is formed by the impingement of a controlled liquid jet at the center of the disk and subsequent radial spreading of liquid along the disk. The chemical reaction between the gas and the liquid film can be expressed as a zero-order homogeneous reaction. The process was modeled by establishing equations for the conservation of mass, momentum, and species concentration and solving them analytically. A scaling analysis was used to determine dominant transport processes. Appropriate boundary conditions were used to solve these equations to develop expressions for the local concentration of gas across the thickness of the film and distributions of film height, bulk concentration, and Sherwood number along the radius of the disk. The partial differential equation for species concentration was solved using the separation of variables technique along with the Duhamel's theorem and the final analytical solution was expressed using confluent hypergeometric functions. Tables for eigenvalues and eigenfunctions are presented for a number of reaction rate constants. A parametric study was performed using Reynolds number, Ekman number, and dimensionless reaction rate as parameters. At all radial locations, Sherwood number increased with Reynolds number (flow rate) as well as Ekman number (rate of rotation). The enhancement of mass transfer due to chemical reaction was found to be small when compared to the case of no reaction (pure absorption), but the enhancement factor was very significant when compared to pure absorption in a stagnant liquid film. The zero-order reaction processes considered in the present investigation included the absorption of oxygen in aqueous alkaline solutions of sodiumdithionite and rhodium complex catalyzed carbonylation of methanol. Present analytical results were compared to previous theoretical results for limiting conditions, and were found to have very good agreement.

S Rajagopalan

Expanding the horizon of bio-naphtha beyond gasoline blend: property characterization and conversion opportunity assessment through technoeconomic and life-cycle analyses

Bio-naphtha, a common by-product of biorefineries, is expected to experience substantial growth in supply due to increasing demands for renewable diesel and synthetic aviation fuel (SAF). However, demand for bio-naphtha itself as a gasoline blendstock is limited because of the electrification of light-duty vehicles. This work investigated valorization opportunities for bio-naphtha from catalytic fast pyrolysis, hydrothermal liquefaction, Fischer–Tropsch synthesis, and hydrotreated esters and fatty acids pathways. These opportunities include producing polymer-grade olefin via steam cracking, SAF via steam cracking followed by olefin oligomerization, and renewable aromatics benzene, toluene, and xylene (BTX) and hydrogen via catalytic reforming. Process models were developed in Aspen Plus V14 and Aspen HYSYS V14 to calculate the mass and energy balances for each conversion step. Technoeconomic assessment and life-cycle analysis were conducted to evaluate the minimum fuel/product selling price, conversion cost, and life-cycle CO2 equivalent (CO2e) emission reduction. Technoeconomic assessment results suggest a minimum fuel/product selling price as low as $1.9/kg of olefins, $6.30/gal of gasoline-equivalent SAF, and $1.2/kg of BTX without any incentives. For all pathways, these prices are dominated by bio-naphtha feedstock costs, which account for at least 76% of the total cost. Compared with petroleum baselines, bio-naphtha-derived SAF, olefins, and BTX can achieve significant CO2e emission reductions from the use of renewable carbon resources. The results of life-cycle analysis and subsequent technoeconomic assessment, incorporating carbon credits, indicate the economic viability of using bio-naphtha for polymer-grade olefin and BTX production, with product costs comparable to market prices.

Xu, Shuang

Well-Defined Iron Sites in Crystalline Carbon Nitride

Carbon nitride materials can be hosts for transition metal sites, but Mössbauer studies on iron complexes in carbon nitrides have always shown a mixture of environments and oxidation states. Here we describe the synthesis and characterization of a crystalline carbon nitride with stoichiometric iron sites that all have the same environment. The material (formula C 6 N 9 H 2 Fe 0.4 Li 1.2 Cl, abbreviated PTI/FeCl 2 ) is derived from reacting poly(triazine imide)·LiCl (PTI/LiCl) with a low-melting FeCl 2 /KCl flux, followed by anaerobic rinsing with methanol. X-ray diffraction, X-ray absorption and Mössbauer spectroscopies, and SQUID magnetometry indicate that there are tetrahedral high-spin iron(II) sites throughout the material, all having the same geometry. As a result, the material is active for electrocatalytic nitrate reduction to ammonia, with a production rate of ca. 0.1 mmol cm –2 h –1 and Faradaic efficiency of ca. 80% at −0.80 V vs RHE.

Anions

Biochemical properties of glycerol kinase from the hypersaline-adapted archaeon Haloferax volcanii

ABSTRACT Extremophilic microorganisms are promising candidates for industrial and analytical biocatalysis.Haloferax volcanii, a halophilic archaeon that prefers glycerol over glucose, channels this substrate into central metabolism through glycerol kinase (GK). Here, we report the biochemical properties ofH. volcaniiGK and its potential for biotechnological applications. An N-terminal His-tagged GK was functionalin vivoand yielded 3 mg/L culture—4.5 times more enzyme than a C-terminal StrepII-tagged version. Size exclusion chromatography revealed a glycerol-induced oligomeric shift from homodimer to a dimer-dominant state with detectable tetramer. The purified enzyme showed robust activity across broad pH and salinity ranges, with optimal activity at 100 mM NaCl and 50°C–60°C. It retained catalytic activity in 5%–10% dimethyl sulfoxide (DMSO) and crude glycerol containing methanol. His-GK was freeze-thaw stable and thermotolerant in 2 M NaCl buffers. In the absence of ligands, the enzyme’s melting temperature (T m ) was 80°C. Glycerol increased the T m to 85°C, and combinations with MgCl₂ (84°C) or ATP (88°C) provided further stabilization. The highest T m (89°C) occurred with all three ligands, suggesting a cumulative stabilizing effect. Kinetic analyses revealed positive cooperativity for glycerol, ATP, and Mg² + ; Mn² + and Co² + also supported the activity.H. volcaniiGK is the first known GK to exhibit positive cooperativity with glycerol and ATP. Its high stability and substrate flexibility support its use in biodiesel waste valorization,in vitrobiocatalysis, and biosensor development—applications demanding robust, specific, and stable enzymes. IMPORTANCE This study reveals thatH. volcaniiGK exhibits positive cooperativity for glycerol, ATP, and Mg² + , a kinetic feature not previously reported for glycerol kinases. This behavior enables steep, switch-like responses to small substrate changes, offering unique advantages for biosensor design. Importantly,H. volcaniiGK also maintains high activity under extreme salinity, temperature, broad pH, and solvent conditions that typically limit enzyme use in industrial and environmental applications. These traits make this GK an ideal candidate for enzyme-based biosensors, which often suffer from poor tolerance to pH, solvent, and thermal stress. Its robustness supports its use in cross-linked enzyme crystals, an immobilization method that enhances enzyme stability and reusability under harsh conditions. Moreover, GKs are already employed in Mg² + detection kits; however,H. volcaniiGK’s ability to tolerate and respond to diverse divalent cations (e.g., Co² + , Mn² + ) broadens their potential for pollutant detection and environmental monitoring. These features collectively positionH. volcaniiGK as a valuable biocatalyst for biosensing,in vitrodiagnostics, and biotechnological applications requiring both precision and durability.

Biotechnology & Applied Microbiology

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