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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Evaluation and beneficiation of high sulfur and high alkali fly ashes for use as supplementary cementitious materials in concrete

Coal-fuel power plants with semi-dry or dry flue gas desulfurization (FGD) systems produce high sulfur and/or high alkali fly ashes due to comingling of fly ash with FGD products. Such fly ashes do not meet the SO 3 content limit (5.0% max.) of ASTM C618 or are unable to mitigate the alkali-silica reaction. The mineralogy of the sulfur present in these ashes can vary significantly (e.g., CaSO 4 , CaSO 3 , Na2SO 4 ) based on the FGD technology used and this affects the performance of these fly ashes in concrete. Thus, the single SO 3 % limit of ASTM C618 is unable to capture the complexity and performance of fly ash, and this results in elimination of potentially viable pozzolans for concrete. Here this study performs a systematic investigation of the effect of SO 3 type and content in fly ash on various performance parameters of cement-fly ash pastes and mortars, including workability (flow and flow retention), pore fluid pH, setting time, strength development, and potential for deleterious expansion. To better quantify and understand these effects, the study considers both real and doped fly ashes (i.e., a blend of specification-compliant fly ash with target sulfur compounds). The poor performance observed in the case of setting time and pore fluid pH was successfully mitigated using chemical admixtures.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Rnf and Fix Have Specific Roles during Aerobic Nitrogen Fixation in Azotobacter vinelandii

Biological nitrogen fixation requires large amounts of energy in the form of ATP and low potential electrons to overcome the high activation barrier for cleavage of the dinitrogen triple bond. The model aerobic nitrogen-fixing bacteria, Azotobacter vinelandii, generates low potential electrons in the form of reduced ferredoxin (Fd) and flavodoxin (Fld) using two distinct mechanisms via the enzyme complexes Rnf and Fix. Both Rnf and Fix are expressed during nitrogen fixation, but deleting either rnf1 or fix genes has little effect on diazotrophic growth. However, deleting both rnf1 and fix eliminates the ability to grow diazotrophically. Rnf and Fix both use NADH as a source of electrons, but overcoming the energetics of NADH's endergonic reduction of Fd/Fld is accomplished through different mechanisms. Rnf harnesses free energy from the chemiosmotic potential, whereas Fix uses electron bifurcation to effectively couple the endergonic reduction of Fd/Fld to the exergonic reduction of quinone. Different reaction stoichiometries and condition-specific differential gene expression indicate specific roles for the two reactions. This work's complementary physiological studies and thermodynamic modeling reveal how Rnf and Fix balance redox homeostasis in various conditions. Specifically, the Fix complex is required for efficient growth under low oxygen concentrations, while Rnf is presumed to maintain reduced Fd/Fld production for nitrogenase under standard conditions. This work provides a framework for understanding how the production of low potential electrons sustains robust nitrogen fixation in various conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

From Nonclassical to Classical: Crystallization Seeds Reshape Nucleation Mechanisms

Crystalline seeds are widely employed in crystallization to accelerate nucleation and control product polymorphs; yet, their impact on nucleation mechanisms remains poorly understood. While homogeneous nucleation of crystals from solution often proceeds through nonclassical pathways involving amorphous intermediates, it is unclear how seeds that promote heterogeneous nucleation reshape these mechanisms and govern polymorph selection. Here, in this study, we provide the first direct evidence that crystalline seeds can bypass the need for amorphous intermediates as nucleation sites, converting nonclassical nucleation mechanisms into classical, monomer-by-monomer crystallization pathways. Using molecular dynamics simulations of zeolite synthesis, we uncover a complex reaction network of competing nucleation processes mediated by intermediate interfacial polymorphs. The interplay between thermodynamic stability and kinetic favorability of these interfacial polymorphs dictates nucleation outcomes, creating a dynamic balance between the interfacial polymorph stability and crystallization rates. Furthermore, we show that the synthesis environment-whether monomers or aggregates serve as reactants-profoundly impacts these pathways. At moderate supersaturation, seeds eliminate amorphous intermediates and promote classical nucleation, whereas high supersaturation or aggregate-based reactants favor nonclassical pathways, even in the presence of seeds. These findings establish a general framework for understanding how seeds govern crystallization mechanisms, with broad implications for controlling nucleation kinetics, polymorph selection, and material properties. While focused on zeolites, this work reveals insights that may be applicable to biominerals, pharmaceuticals, functional materials, and catalysts, providing a basis for engineering crystallization pathways in diverse applications.

Chu-Jon, Carlos [Univ. of Utah, Salt Lake City, UT↗
DOE OSTI2021

The radioactive nuclei 26 Al and 60 Fe in the Cosmos and in the solar system

The cosmic evolution of the chemical elements from the Big Bang to the present time is driven by nuclear fusion reactions inside stars and stellar explosions. A cycle of matter recurrently re-processes metal-enriched stellar ejecta into the next generation of stars. The study of cosmic nucleosynthesis and this matter cycle requires the understanding of the physics of nuclear reactions, of the conditions at which the nuclear reactions are activated inside the stars and stellar explosions, of the stellar ejection mechanisms through winds and explosions, and of the transport of the ejecta towards the next cycle, from hot plasma to cold, star-forming gas. Due to the long timescales of stellar evolution, and because of the infrequent occurrence of stellar explosions, observational studies are challenging, as they have biases in time and space as well as different sensitivities related to the various astronomical methods. Here, we describe in detail the astrophysical and nuclear-physical processes involved in creating two radioactive isotopes useful in such studies, 26 Al and 60 Fe. Due to their radioactive lifetime of the order of a million years, these isotopes are suitable to characterise simultaneously the processes of nuclear fusion reactions and of interstellar transport. We describe and discuss the nuclear reactions involved in the production and destruction of 26 Al and 60 Fe, the key characteristics of the stellar sites of their nucleosynthesis and their interstellar journey after ejection from the nucleosynthesis sites. This allows us to connect the theoretical astrophysical aspects to the variety of astronomical messengers presented here, from stardust and cosmic-ray composition measurements, through observation of γ rays produced by radioactivity, to material deposited in deep-sea ocean crusts and to the inferred composition of the first solids that have formed in the Solar System. We show that considering measurements of the isotopic ratio of 26 Al to 60 Fe eliminate some of the unknowns when interpreting astronomical results, and discuss the lessons learned from these two isotopes on cosmic chemical evolution. This review paper has emerged from an ISSI-BJ Team project in 2017–2019, bringing together nuclear physicists, astronomers, and astrophysicists in this inter-disciplinary discussion.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Native lattice strain induced structural earthquake in sodium layered oxide cathodes

Abstract High-voltage operation is essential for the energy and power densities of battery cathode materials, but its stabilization remains a universal challenge. To date, the degradation origin has been mostly attributed to cycling-initiated structural deformation while the effect of native crystallographic defects induced during the sophisticated synthesis process has been significantly overlooked. Here, using in situ synchrotron X-ray probes and advanced transmission electron microscopy to probe the solid-state synthesis and charge/discharge process of sodium layered oxide cathodes, we reveal that quenching-induced native lattice strain plays an overwhelming role in the catastrophic capacity degradation of sodium layered cathodes, which runs counter to conventional perception—phase transition and cathode interfacial reactions. We observe that the spontaneous relaxation of native lattice strain is responsible for the structural earthquake (e.g., dislocation, stacking faults and fragmentation) of sodium layered cathodes during cycling, which is unexpectedly not regulated by the voltage window but is strongly coupled with charge/discharge temperature and rate. Our findings resolve the controversial understanding on the degradation origin of cathode materials and highlight the importance of eliminating intrinsic crystallographic defects to guarantee superior cycling stability at high voltages.

25 ENERGY STORAGE↗
DOE OSTI2023

Interplay between copper redox and transfer and support acidity and topology in low temperature NH 3 -SCR

Low-temperature standard NH 3 -SCR over copper-exchanged zeolite catalysts occurs on NH 3 -solvated Cu-ion active sites in a quasi-homogeneous manner. As key kinetically relevant reaction steps, the reaction intermediate Cu II (NH 3 ) 4 ion hydrolyzes to Cu II (OH)(NH 3 ) 3 ion to gain redox activity. The Cu II (OH)(NH 3 ) 3 ion also transfers between neighboring zeolite cages to form highly reactive reaction intermediates. Via operando electron paramagnetic resonance spectroscopy and SCR kinetic measurements and density functional theory calculations, we demonstrate here that such kinetically relevant steps become energetically more difficult with lower support Brønsted acid strength and density. Consequently, Cu/LTA displays lower Cu atomic efficiency than Cu/CHA and Cu/AEI, which can also be rationalized by considering differences in their support topology. By carrying out hydrothermal aging to eliminate support Brønsted acid sites, both Cu II (NH 3 ) 4 ion hydrolysis and Cu II (OH)(NH 3 ) 3 ion migration are hindered, leading to a marked decrease in Cu atomic efficiency for all catalysts.

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

Ligand Influence on Indium–Sulfide Cluster Formation and Reactivity

An indium–sulfide tetramer ([InMe 2 (SSiMe 3 )] 4 ), which contains reactive silyl and methyl groups, is shown to be an isolable intermediate in cluster synthesis. The reactive groups allow it to act as a synthon in the formation of multinuclear indium–sulfide architectures, evidenced by the crystallization of a coordination polymer ([In 20 S 14 Me 32 (4,4’-bpy) 5 ·5CH 2 Cl 2 ] n ) utilizing In 10 S 7 clusters as nodes. The reaction between trimethylindium (InMe 3 ) and bis­(trimethylsilyl)­sulfide (S­(SiMe 3 ) 2 ) is explored with and without the presence of a ligating bipyridine. In both cases, a sulfide-indium adduct is formed, which slowly converts into a multimetallic complex. Here, the ligand 2,2’-bipyridine (2,2’-bpy) is coordinated to InMe 3 to form the adduct InMe 3 (bpy), which upon addition of sulfide, eliminates tetramethylsilane (TMS) and binds two additional InMe 3 moieties (InMe 2 (bpy)­(μ 3 -SSiMe 3 )­(InMe 3 ) 2 ). When reacted neatly without bipyridine, InMe 3 and S­(SiMe 3 ) 2 form the adduct InMe 3 (S­(SiMe 3 ) 2 ), which subsequently eliminates TMS and intermolecularly associates to yield [InMe 2 (SSiMe 3 )] 4 . Although stable in an inert atmosphere, [InMe 2 (SSiMe 3 )] 4 undergoes facile hydrolysis to yield [InMeS] n when exposed to air. The effect of ligand addition (4,4’-bipyridine (4,4’-bpy)) to [InMe 2 (SSiMe 3 )] 4 is then examined. In every case, it is shown that the presence of the bpy ligand has a profound influence on the resulting structure, as shown by the unexpected formation of a trimer and In 10 S 7 cluster network.

Bell, Colby Seth [Argonne National Laboratory (ANL↗
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 OSTI2019

Moisture Corrosion of LiH: A Kinetic Investigation by DRIFT Spectroscopy

Lithium hydride (LiH) is a unique, ionic compound with applications in a variety of industries. Unfortunately, LiH is very reactive toward H 2 O even at ppm levels, forming oxide (Li 2 O) and hydroxide (LiOH) corrosion layers while outgassing H 2 . An effective means to eliminate unwanted outgassing is vacuum-heating to convert LiOH into Li 2 O, although subsequent re-exposure to moisture during transport/handling reconverts some Li 2 O back to LiOH. A corrosion growth model for previously vacuum-baked LiH is necessary for long-term prediction of the hydrolysis of LiH. In this work, a para-linear hydroxide corrosion growth model is proposed for the reaction of previously vacuum-baked LiH samples with moisture. This model, composed of two competing diffusion reaction fronts at the LiOH/Li 2 O and Li 2 O/LiH interfaces, is validated experimentally by subjecting a previously vacuum-baked polycrystalline LiH sample to 35 ppm of H 2 O at room temperature while monitoring the corrosion growth as a function of time with diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy. The para-linear growth model for the hydrolysis of previously vacuum-baked LiH proposed in this report can also serve as a template for the hydrolysis of other hygroscopic oxides grown on metal or metal hydride substrates.

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

Solar Thermochemical Ammonia Production (STAP) (Final Report)

Ammonia (NH 3 ) is an energy-dense chemical and a vital component of fertilizer. In addition, it is a carbon-neutral liquid fuel and a potential candidate for thermochemical energy storage for high-temperature concentrating solar power (CSP). Currently, NH 3 synthesis occurs via the Haber-Bosch process, which requires high pressures (15-25 MPa) and medium to high temperatures (400-500 °C). N 2 and H 2 are essential feedstocks for this NH 3 production process. H 2 is generally derived from methane via steam reforming; N 2 is sourced from air, after oxygen removal via combustion of hydrocarbons. Both processes consume hydrocarbons, resulting in the release of CO 2 . In addition, hydrocarbon fuels are burned to produce the heat and mechanical energy required to perform the NH 3 reaction, further increasing CO 2 emissions. Overall, the production of ammonia via the Haber-Bosch (H-B) process is responsible for up to 1.4% of the world’s carbon emissions. The development of a renewable pathway to NH 3 synthesis, which utilizes concentrated solar irradiation as a process heat instead of fossil fuels and operates under low or ambient pressure, will result in a decrease (or elimination) of greenhouse gas emissions as well as avoid the cost, complexity, and safety issues inherent in high-pressure processes. Most current efforts to “green” ammonia production involve either electrolysis or simply replacing the energy source for H-B with renewable electricity, but otherwise leaving the process intact. The effort proposed here would create a new paradigm for the synthesis of NH 3 utilizing solar-thermal heat, water, and air as feedstocks, providing a truly green method of production. The overall objective of the STAP (Solar Thermal Ammonia Production) project was to develop a solar thermochemical looping technology to produce and store nitrogen (N 2 ) from air for the subsequent production of ammonia (NH 3 ) via an advanced two-stage process. The goal is a cost-effective and energy efficient technology for the renewable N 2 production and synthesis of NH 3 from H 2 (produced from H 2 O) and air using solar-thermal energy from concentrating sunlight, under pressures an order of magnitude lower than H-B NH 3 production. Our process involves two looping cycles, which do not require catalysts and can be recycled. Over the course of the STAP project, we (1) developed and deeply characterized oxide materials for N 2 separation; (2) developed a method for the synthesis of metal nitrides, producing a series of quaternary compounds that have been heretofore unreported; (3) modeled, designed, and fabricated bench-scale tube and on-sun reactors for the N 2 production step and demonstrated the ability to separate N 2 over multiple cycles in the tube reactor; (4) designed and fabricated a bench-scale Ammonia Synthesis Reactor (ASR) and demonstrated the proof of concept of NH 3 synthesis via a novel looping process using metal nitrides over multiple cycles; and (5) completed a systems- and technoeconomic analysis showing the feasibility of ammonia production on a larger scale via the STAP process. The development of renewable, low-cost NH 3 will be of great interest to the chemicals industry, particularly agricultural sectors. The CSP industry should be both an important customer and potential end-user of this technology, as it affords the capability of synthesizing a promising thermochemical storage material on-site. Since the NH 3 synthesis step also requires H 2 , there will exist a symbiotic relationship between this technology and solar-thermochemical water-splitting applications. Green ammonia synthesis will result in the decarbonization of a hydrocarbon-intensive industry, helping to meet the Administration goal of industrial decarbonization by 2050. The resulting decrease in CO 2 and related pollutants will improve health and well-being of society, particularly for those living in the vicinity of commercial production plants.

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

Vitamin-Mediated Glucose Flow Cell for Sustainable Power Generation

Glucose as biofuel asserts unique advantages, including low-temperature electricity generation, easy accessibility, low storage cost, and flexible application for on-demand power generation. Riboflavin, also known as Vitamin B 2 , is a critical component in biological systems and is involved in many metabolic reactions as enzyme cofactors. Inspired by these metabolic reactions, we demonstrate a flow cell for electrochemical glucose oxidation reaction (GOR), using riboflavin as an environmentally friendly mediator to replace traditional noble metal catalysts. When paired with O 2 under alkaline conditions, the glucose flow cell achieves a peak power density of 13 mW/cm 2 , 20 times higher than the previous report in alkaline conditions. The demonstrated vitamin-mediated engineered biofuel flow cell delivered high peak power density at room temperature/ambient pressure while maintaining low cost and environmental friendliness, eliminating the need for a noble metal catalyst.

electrolytes↗
DOE OSTI2021

A Genome-Scale Metabolic Model of Anabaena 33047 to Guide Genetic Modifications to Overproduce Nylon Monomers

Nitrogen fixing-cyanobacteria can significantly improve the economic feasibility of cyanobacterial production processes by eliminating the requirement for reduced nitrogen. Anabaena sp. ATCC 33047 is a marine, heterocyst forming, nitrogen fixing cyanobacteria with a very short doubling time of 3.8 h. We developed a comprehensive genome-scale metabolic (GSM) model, iAnC892, for this organism using annotations and content obtained from multiple databases. iAnC892 describes both the vegetative and heterocyst cell types found in the filaments of Anabaena sp. ATCC 33047. iAnC892 includes 953 unique reactions and accounts for the annotation of 892 genes. Comparison of iAnC892 reaction content with the GSM of Anabaena sp. PCC 7120 revealed that there are 109 reactions including uptake hydrogenase, pyruvate decarboxylase, and pyruvate-formate lyase unique to iAnC892. iAnC892 enabled the analysis of energy production pathways in the heterocyst by allowing the cell specific deactivation of light dependent electron transport chain and glucose-6-phosphate metabolizing pathways. The analysis revealed the importance of light dependent electron transport in generating ATP and NADPH at the required ratio for optimal N2 fixation. When used alongside the strain design algorithm, OptForce, iAnC892 recapitulated several of the experimentally successful genetic intervention strategies that over produced valerolactam and caprolactam precursors.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Iron Oxide Reduction Rate Affects Iron Product Morphology

Magnetite concentrates from different parts of the Mesabi Range, exhibiting varying tendencies to encapsulate, were reduced using thermogravimetric analysis (TGA) and a high-temperature confocal scanning laser microscope (CSLM). Gas-phase mass-transfer conditions were intentionally varied by employing two reactors with different geometries: the TGA produced significantly slower reduction, whereas the CSLM setup yielded reduction rates up to 20 times faster under mass-transfer-controlled conditions. A preliminary mechanism is proposed to explain the transition from a porous iron product to a dense encapsulating layer. Encapsulation is interpreted as the outcome of competition between pore creation, driven by the reduction rate, and pore elimination, driven by surface diffusion. When pore formation is insufficient to counteract pore coarsening, a dense iron layer develops and restricts further reduction.

encapsulation↗
DOE OSTI2024

Deep exclusive meson production as a probe to the puzzle of Λ hyperon polarization

In the 1970s, an unexpected transverse Λ polarization in unpolarized proton-beryllium collisions was discovered, which initiated extensive studies on spin phenomena in high-energy physics. Over the past five decades, similar transverse Λ polarization has been observed across various collision systems, including lepton-hadron deep-inelastic scattering, hadron-hadron collisions, and electron-positron collisions. Despite numerous promising theoretical models, the fundamental mechanism underlying this polarization phenomenon remains inconclusive to this day. However, in both longitudinally and transversely polarized lepton-hadron and hadron-hadron collisions, it is found that the Λ hyperon is polarized with respect to the initial parton spin direction. How the Λ hyperon acquires its spin has become one of the most crucial questions to address in order to resolve this puzzle. In this paper, I propose to use an exclusive process that can be measured at the Electron-Ion Collider, the deep exclusive meson production, to explicitly test the mechanism of Λ polarization. The outcomes of this experimental measurement are anticipated to unveil the dominant mechanism by which Λ obtains its spin, eliminating many of the ambiguities that have been encountered in previous studies. Finally, experimental challenges and requirements are discussed. Published by the American Physical Society 2024

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Understanding NBI heating and fueling in LTX-β tokamak

My work on the contract DE-SC=0023274 (July, 2022 - July, 2025) was focused on understanding the plasma fueling by NBI. On Dec. 1998 with Sergei Krasheninnikov (UCSD, San Diego, CA) we initiated the Li Wall Fusion (LiWFusion) as a new concept of magnetic fusion [1]. The new 1 2 plasma 3 4 5 6 2.1 Overview of rate coefficients, mean-free paths λH0 , and diffusions coefficients 6 2. GSV code for ⟨σv⟩ analysis of NBI fueling concept was a reaction of the lack of luck of tokamak fusion with QDT = 1 on TFTR and JET. We recognized the edge plasma cooling by recycling to be the route reason of the tokamak problems on the way to burning plasma. LiWFusion relies on plasma pumping by a lithium layer on the inner walls of the plasma chamber, combined with the plasma heating and fueling by the Neutral Beam Injection (NBI). These two innovations eliminate the route problem of the tokmak fusion. The concept became theoretically mature in 2006. In 2012, the technology of continuously Flowing Liquid Lithium (24/7-FLiLi) was invented by me for the future implementations of the LWFusion concept. At the same time, my every presentation on LiWFusion to International Symposium on Lithium Applications since 2010 was objected by some person with words “Everybody since the 1970s knows that plasma fueling by NBI is impossible”. I dropped the name of the author of this objection and ignored his views. My work on the current grant on NBI fueling of LTX-β not only clarified the issue but resolved it in an astonishing way. The NBI fueling was fully understood (thus humiliating the current dogmatic fusion community). The new future of LTX-β dedicated for decades to Li in tokamaks, as well as of the entire magnetic fusion program was envisioned, in sharp contrast with the fallure of OFES in the post-TFTR era of 21st century.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Scalable Synthesis of 2D Mo 2 C and Thickness‐Dependent Hydrogen Evolution on Its Basal Plane and Edges

Abstract 2D transition metal carbides (2D TMCs and MXenes) are promising candidates for applications of energy storage and catalysis. However, producing high‐quality, large 2D flakes of Mo2C MXene has been challenging. Here, a new salt‐assisted templating approach is reported that enables the direct synthesis of 2D Mo 2 C with low defect concentrations. KCl acts as a template to form an intermediate 2D product, facilitating Mo 2 C formation without coarsening upon melting. The thickness of the flakes produced can range from monolayer (0.36 nm) to 10 layers (4.55 nm), and the electrocatalytical hydrogen evolution reaction (HER) activity of 2D Mo 2 C is inversely proportional to its thickness. The monolayer Mo 2 C shows remarkable HER performance with a current density of ≈6800 mA cm − 2 at 470 mV versus reversible hydrogen electrode and an ultrahigh turnover frequency of ≈17 500 s − 1 . This salt‐assisted synthesis approach can also produce WC and V 8 C 7 nanosheets, expanding the family of 2D carbides. The new pathway eliminates the need for layered ceramic precursors, making it a versatile approach to direct synthesis of MXene‐like 2D carbides.

Chemistry↗
DOE OSTI2020

Nickel–Mediated Trifluoromethylation of Phenol Derivatives by Aryl C–O Bond Activation

The increasing pharmaceutical importance of trifluoromethylarenes has stimulated the development of more efficient trifluoromethylation reactions. Tremendous efforts have focused on copper– and palladium–mediated/catalyzed trifluoromethylation of aryl halides. In contrast, no general method exists for the conversion of widely available inert electrophiles, such as phenol derivatives, into the corresponding trifluoromethylated arenes. Reported herein is a practical nickel–mediated trifluoromethylation of phenol derivatives with readily available trimethyl(trifluoromethyl)silane (TMSCF 3 ). The strategy relies on PMe 3 –promoted oxidative addition and transmetalation, and CCl 3 CN–induced reductive elimination. Here, the broad utility of this transformation has been demonstrated through the direct incorporation of trifluoromethyl into aromatic and heteroaromatic systems, including biorelevant compounds.

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

Rapid Polyolefin Plastic Hydrogenolysis Mediated by Single-Site Heterogeneous Electrophilic/Cationic Organo-group IV Catalysts

A homologous series of cationic electrophilic group IV metal hydrides (M = Ti, Zr, Hf) created by chemisorption of the corresponding MNp 4 precursors on highly Brønsted acidic sulfated alumina (AlS) to yield loosely coordinated surface AlS/MNp 2 (Np = neopentyl) species are systematically characterized by ICP, EXAFS/XANES, DRIFTS, and solid-state high-resolution multidimensional NMR spectroscopy (SSNMR), as well as by energy span DFT computation. With effective stirring, these complexes readily undergo reaction with H 2 to yield AlS/M(alkyl)H species, which are highly active for the hydrogenolysis of diverse commercial polyethylenes, α-olefin-ethylene copolymers, isotactic polypropylene, and postconsumer polyolefins including high-density polyethylenes, yielding medium and small linear and branched hydrocarbons at turnover frequencies as high as 36,300 h –1 at 200 °C/17 atm H 2 for M = Zr. For given polyolefin and reaction conditions, turnover frequencies scale approximately as M = Zr > Hf > Ti, whereas catalyst thermal stability scales approximately as M = Hf ≈ Zr > Ti, and these trends are qualitatively understandable from the DFT analysis. These catalytic results reveal that the AlS/Hf(R)H-mediated hydrogenolysis favors wax-like and liquid products, whereas the AlS/Zr(R)H-mediated hydrogenolysis can be tuned between gases and liquids. Finally, DFT analysis identifies β-alkyl elimination as the turnover-limiting C–C scission process, which is particularly facile in these cationic d 0 complexes but not so in the neutrally charged analogues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗