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Interaction energies from scattering cross section of hydrogen ions in methane, ethane, carbon tetrafluoride, and hexafluoroethane
Interaction energies from scattering cross section of hydrogen ions in methane, carbon tetrafluoride, ethane, and hexafluoroethane
The Composite Infrared Spectrometer observed Jupiter in the thermal infrared during the swing-by of the Cassini spacecraft. Results include the detection of two new stratospheric species, the methyl radical and diacetylene, gaseous species present in the north and south auroral infrared hot spots; determination of the variations with latitude of acetylene and ethane, the latter a tracer of atmospheric motion; observations of unexpected spatial distributions of carbon dioxide and hydrogen cyanide, both considered to be products of comet Shoemaker-Levy 9 impacts; characterization of the morphology of the auroral infrared hot spot acetylene emission; and a new evaluation of the energetics of the northern auroral infrared hot spot.
We present a re‐examination of mass spectral data obtained from the Pioneer Venus Large Probe Neutral Mass Spectrometer. Our interpretations of differing trace chemical species are suggestive of redox disequilibria in Venus' middle clouds. Assignments to the data (at 51.3 km) include phosphine, hydrogen sulfide, nitrous acid, nitric acid, carbon monoxide, hydrochloric acid, hydrogen cyanide, ethane, and potentially ammonia, chlorous acid, and several tentative PxOy species. All parent ions were predicated upon assignment of corresponding fragmentation products, isotopologues, and atomic species. The data reveal parent ions at varying oxidation states, implying the presence of reducing power in the clouds, and illuminating the potential for chemistries yet to be discovered. When considering the hypothetical habitability of Venus' clouds, the assignments reveal a potential signature of anaerobic phosphorus metabolism (phosphine), an electron donor for anoxygenic photosynthesis (nitrite), and major constituents of the nitrogen cycle (nitrate, nitrite, ammonia, and N2).
The 2016 Billion-Ton Report (BT16), Volume 2: Environmental Sustainability Effects of Select Scenarios from Volume 1, jointly released by the U.S. Department of Energy's Bioenergy Technologies Office (BETO) and Oak Ridge National Laboratory (ORNL), is a pioneering effort to analyze a range of potential environmental effects associated with illustrative near-term and long-term biomass-production scenarios from the 2016 Billion-Ton Report, Volume 1. This chapter of the 2016 Billion-Ton Report, Volume 2, was authored by NREL researchers Ethan Warner, Yimin Zhang, Danny Inman, Annika Eberle, Alberta Carpenter, Garvin Heath, and Dylan Hettinger.
The Arctic Methane, Carbon Aerosols, and Tracers Study was a measurement campaign at the National Oceanic and Atmospheric Administration (NOAA) Barrow Observatory and U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility North Slope of Alaska (NSA) sites in Barrow (formerly known as Utqiagvik) that involved the deployment of instruments to measure CH4, black carbon (BC), and source tracers. The campaign ran from September 1, 2014 to September 1, 2016 and was extended until July 30, 2017. We deployed an in situ instrument to measure methane, the ratio of its isotopologues 13CH4/12CH4, and ethane. We deployed a second instrument to measure carbon monoxide, carbonyl sulfide (COS), carbon dioxide, and water vapor. We also deployed an in situ instrument to measure BC, a single-particle soot photometer (SP2), at the nearby NOAA Barrow Observatory, co-located with the other NOAA aerosol instruments. Changes in emissions across different regions and seasons will be inferred using atmospheric transport and inverse modeling techniques.
Here, we develop a one-dimensional analytical solution based on the method of characteristics to explore hydrate formation from gas injection into brine-saturated sediments within the hydrate stability zone. Our solution includes fully coupled multiphase and multicomponent flow and the associated advective transport in a homogeneous system. Our solution shows that hydrate saturation is controlled by the initial thermodynamic state of the system and changed by the gas fractional flow. Hydrate saturation in gas-rich systems can be estimated by 1 – cl 0 /cl e when Darcy flow dominates, where cl 0 is the initial mass fraction of salt in brine, and cl e is the mass fraction of salt in brine at three-phase (gas, liquid, and hydrate) equilibrium. Hydrate saturation is constant, gas saturation and gas flux decrease, and liquid saturation and liquid flux increase with the distance from the gas inlet to the hydrate solidification front. The total gas and liquid flux is constant from the gas inlet to the hydrate solidification front and decreases abruptly at the hydrate solidification front due to gas inclusion into the hydrate phase. The advancing velocity of the hydrate solidification front decreases with hydrate saturation at a fixed gas inflow rate. This analytical solution illuminates how hydrate is formed by gas injection (methane, CO 2 , ethane, propane) at both the laboratory and field scales.
The lithium–sulfur energy storage system has the potential to deliver high energy density for grid and transportation applications. Lithium polysulfides (LiPS) formed during the chemical transformation of elemental sulfur can be reactive toward commonly used ether solvents. In this chapter, using density functional theory calculations, we address kinetic and thermodynamic feasibilities of LiPS reactions with various ether molecules (linear and cyclic) and fluorine-substituted ether molecules to understand their long-term chemical stability as solvents or cosolvents. These a priori computations indicate that the most reactive intermediates that initiate a likely degradation reaction of ether solvent molecules are Li2S2, Li2S3, Li2S4, and S2 2−. The lowest computed activation barriers (ΔH ‡) for the CO bond cleavage of dimethoxy ethane (DME) by shorter chain polysulfides or sulfide anions are in the range of ∼27–35 kcal mol−1, suggesting extremely slow kinetics for a polysulfide-induced ether solvent degradation. Calculations are extended to nine more linear and cyclic ether solvent molecules including the glymes, tetrahydrofuran (THF), and dioxolane (DOL). Computations suggest that the solvent stability is higher for shorter chain linear ethers compared to longer chain linear ethers and cyclic ethers. In addition to the 10 ether solvent candidates, simulations were also performed to understand the kinetic stability of 16 fluorinated DME molecules – a model for fluorinated ether species. Computations show that the introduction of one or more CF bond(s) in linear ether molecules enables nucleophilic attack by the polysulfide species, especially toward the polar CF/CO bonds. The CO bond stability of the fluoroether molecule was also compromised by the presence of the highly electron-withdrawing “−F” functional group. In general, in this chapter, utilizing the predictive power of first principle simulations, the LiPS reactivity toward ether solvent molecules was simulated and likely reactions that cause degradation are discussed. These studies also provide guidelines for the design of electrolyte systems with longer term chemical stability.
Abstract The lifespan of lithium (Li) metal batteries (LMBs) can be greatly improved by the formation of inorganic‐rich electrode‐electrolyte interphases (EEIs) (including solid‐electrolyte interphase on anode and cathode‐electrolyte interphase on cathode). In this work, a localized high‐concentration electrolyte containing lithium bis(fluorosulfonyl)imide (LiFSI) salt, 1,2‐dimethoxyethane (DME) solvent and 1,2‐bis(1,1,2,2‐tetrafluoroethoxy)ethane (BTFEE) diluent is optimized. BTFEE is a fluorinated ether with weakly‐solvating ability for LiFSI so it also acts as a co‐solvent in this electrolyte. It can facilitate anion decomposition at electrode surfaces and promote the formation of more inorganic‐rich EEI layers. With an optimized molar ratio of LiFSI:DME:BTFEE = 1:1.15:3, LMBs with a high loading (4 mAh cm −2 ) lithium nickel manganese cobalt oxide (LiNi 0.8 Mn 0.1 Co 0.1 ) cathode can retain 80% capacity in 470 cycles when cycled in a voltage range of 2.8–4.4 V. The fundamental understanding on the functionality of BTFEE revealed in this work provides new perspectives on the design of practical high‐energy density battery systems.
Abstract The semi‐hydrogenation of acetylene in ethylene‐rich gas streams is a high‐priority industrial chemical reaction for producing polymer‐grade ethylene. Traditional thermocatalytic routes for acetylene reduction to ethylene, despite progress, still require high temperatures and high H 2 consumption, possess relatively low selectivity, and use a noble metal catalyst. Light‐powered strategies are starting to emerge, given that they have the potential to use directly the abundant and sustainable solar irradiation, but are ineffective. Here an efficient, >99.9% selective, visible‐light powered, catalytic conversion of acetylene to ethylene is reported. The catalyst is a homogeneous molecular cobaloxime that operates in tandem with a photosensitizer at room temperature and bypasses the use of non‐environmentally friendly and flammable H 2 gas feed. The reaction proceeds through a cobalt‐hydride intermediate with ≈100% conversion of acetylene under competitive (ethylene co‐feed) conditions after only 50 min, and with no evolution of H 2 or over‐hydrogenation to ethane. The cobaloxime is further incorporated as a linker in a metal–organic framework; the result is a heterogeneous catalyst for the conversion of acetylene under competitive (ethylene co‐feed) conditions that can be recycled up to six times and remains catalytically active for 48 h, before significant loss of performance is observed.
Chemicals based products and the processes that manufacture them play important roles in sustaining our society. Chemical, biochemical, petrochemical and related processes are characterized by either conversion of specific raw materials to desired chemicals or extraction of desired chemicals from specific raw materials. Well–known examples in the first category are the conversion of methanol and acetic acid to form methyl acetate and water, and, carbon dioxide hydrogenation to methanol via the reverse water gas shift reaction. In the second category, the use of de–methanizer, de–ethanizer, de–propanizer, and so on, separation steps in gas processing plants are well–known. In the conversion–based processes, as the conversions of raw materials are usually not 100% complete, energy intensive downstream separation techniques need to be employed to separate the desired products and recycle the unreacted raw materials. Note that the conversion process itself may also be energy intensive. In the extraction–based processes where product chemicals do not usually represent 100% of the raw material, energy intensive separation techniques are commonly employed to achieve the desired separations. This means that for both categories of processes, energy in different forms need to be supplied and the processes during operation have the potential to produce waste that may lead to negative environmental impacts and cause supply chain issues. Furthermore, planet earth is facing challenges with respect to energy, water, food, and environment, and significant improvements in process efficiencies of new and/or existing processes are needed.
We will discuss recent results from our group in reacting CO 2 and light alkanes to produce syngas, olefins, aromatics, and oxygenates. We will mainly use the simultaneous upgrading of CO 2 and ethane (SU-CO 2 Et) as examples to demonstrate the feasibility and reaction pathways of these processes. We will briefly discuss synthesis methods and essential structural characterization techniques that can be applied to SU-CO 2 Et catalysts. We will then illustrate how to identify and apply distinct active sites for different upgrading processes, using a combination of kinetic studies, in situ characterization, and density functional theory (DFT) calculations. We will conclude the Perspective by pointing out challenges and potential directions in catalyst design and synthesis, as well as structural characterization and mechanistic investigations, to further advance the simultaneous upgrading of CO 2 and light alkanes.
Abstract Raw natural gas is a complex mixture comprising methane, ethane, other hydrocarbons, hydrogen sulfide, carbon dioxide, nitrogen, and water. For sour gas fields, selective and energy‐efficient removal of H 2 S is one of the crucial challenges facing the natural‐gas industry. Separation using nanoporous materials, such as zeolites, can be an alternative to energy‐intensive amine‐based absorption processes. Herein, the adsorption of binary H 2 S/CH 4 and H 2 S/C 2 H 6 mixtures in the all‐silica forms of 386 zeolitic frameworks is investigated using Monte Carlo simulations. Adsorption of a five‐component mixture is utilized to evaluate the performance of the 16 most promising materials under close‐to‐real conditions. It is found that depending on the fractions of CH 4 , C 2 H 6 , and CO 2 , different sorbents allow for optimal H 2 S removal and hydrocarbon recovery.
Abstract DDT (1,1,1‐trichloro‐2,2‐bis(4‐chlorophenyl)ethane), a contact insecticide with a rich and controversial history since its activity was discovered in 1939, has long been thought to be monomorphic. Herein we report the discovery and characterization of a second polymorph, designated Form II, which can be isolated as single crystals, but converts very slowly at room temperature to the form reported previously, now designated as Form I. Computations based on an evolutionary algorithm for crystal structure prediction revealed that Forms I and II are among the four lowest energy crystal structures of fifty calculated. A preliminary study of the contact insecticidal activity toward fruit flies (Drosophila melanogaster) indicates that Form II is more active, suggesting opportunities for more effective solid‐state formulations that would allow reduced amounts of DDT, thereby minimizing environmental impact.
Abstract We report the characterization of an S = iron π‐complex, [Fe(η 6 ‐IndH)(depe)] + (Ind=Indenide (C 9 H 7 − ), depe=1,2‐bis(diethylphosphino)ethane), which results via C−H elimination from a transient Fe III hydride, [Fe(η 3 :η 2 ‐Ind)(depe)H] + . Owing to weak M−H/C−H bonds, these species appear to undergo proton‐coupled electron transfer (PCET) to release H 2 through bimolecular recombination. Mechanistic information, gained from stoichiometric as well as computational studies, reveal the open‐shell π‐arene complex to have a BDFE C‐H value of ≈50 kcal mol −1 , roughly equal to the BDFE Fe‐H of its Fe III −H precursor (Δ G °≈0 between them). Markedly, this reactivity differs from related Fe(η 5 ‐Cp/Cp*) compounds, for which terminal Fe III −H cations are isolable and have been structurally characterized, highlighting the effect of a benzannulated ring (indene). Overall, this study provides a structural, thermochemical, and mechanistic foundation for the characterization of indenide/indene PCET precursors and outlines a valuable approach for the differentiation of a ring‐ versus a metal‐bound H‐atom by way of continuous‐wave (CW) and pulse EPR (HYSCORE) spectroscopic measurements.
Abstract Reversible catalysis is a hallmark of energy‐efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition‐state barriers. Using these criteria, we demonstrate reversible CO 2 /HCO 2 − conversion catalyzed by [Pt(depe) 2 ] 2+ (depe=1,2‐ bis (diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO 2 reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50 mV overpotential. We also find that for CO 2 reduction, H 2 evolution is negligible and the Faradaic efficiency for HCO 2 − production is nearly quantitative. A free‐energy analysis reveals H 2 evolution is endergonic, providing a thermodynamic basis for highly selective CO 2 reduction.
Abstract Using a mechanism‐based solvent‐free tandem catalytic approach, commodity polyester plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN) are rapidly and selectively deconstructed by combining the two air‐ and moisture‐stable catalysts, Hf(OTf) 4 and Pd/C, under 1 atm H 2 , affording terephthalic acid (or naphthalene dicarboxylic acid for PEN) and ethane (or butane for PBT) in essentially quantitative yield. This process is effective for both laboratory grade and waste plastics, and comingled polypropylene remains unchanged. Combined experimental and DFT mechanistic analyses indicate that Hf(OTf) 4 catalyzes a mildly exergonic retro‐hydroalkoxylation reaction in which an alkoxy C−O bond is first cleaved, yielding a carboxylic acid and alkene, and this process is closely coupled to an exergonic olefin hydrogenation step, driving the overall reaction forward.
Abstract Because C 2 H 4 plays an essential role in the chemical industry, economical and energy‐efficient separation of ethylene (C 2 H 4 ) from ethane (C 2 H 6 ) is extremely important. With the exception of energy‐intensive cryogenic distillation, there are few one‐step methods to obtain polymer‐grade (≥99.95 % pure) C 2 H 4 from C 2 H 4 /C 2 H 6 mixtures. Here we report a highly stable metal‐organic‐framework (MOF) FJI‐H11‐Me(des) (FJI‐H=Hong's group in Fujian Institute of Research on the Structure of Matter) which features one‐dimensional hexagonal nonpolar pore surfaces constructed by aromatic rings and alkyl groups. This FJI‐H11‐Me(des) adsorbs C 2 H 6 rather than C 2 H 4 between 273 and 303 K. Practical breakthrough experiments with C 2 H 4 containing 1 % C 2 H 6 have shown that FJI‐H11‐Me(des) can realize the acquisition in one‐step of polymer‐grade, 99.95 % pure C 2 H 4 under various conditions including different gas flow rates, temperatures and relative humidity.