Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “CONTAINER”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Solidification behavior and cracking mechanisms of Ru-containing BCC-B2 superalloys

Many precipitation-strengthened alloys are highly susceptible to cracking during additive manufacturing (AM), which often requires compositional adjustments to mitigate. Recently, it has been demonstrated that refractory BCC alloys can be precipitation strengthened with ordered Ru-containing B2 precipitates to temperatures exceeding 1200 °C. This motivates a study of the potential fabricability of quaternary and quinary refractory BCC-B2 alloys by AM using single track laser experiments. Alloys with greater than 9 at.% Ru exhibit crack formation upon cooling. Solidification cracking was observed in all Zr-containing alloys, which can be mitigated by substituting Hf. Furthermore, this cracking is attributed to the strong partitioning of Zr during solidification, as revealed by characterization of alloy solidus, liquidus, and partition coefficients. Hf 5 Ru 4 -Nb 63 V 28 is identified as a promising BCC-B2 composition with a high B2 solvus (>1300 °C) and solidus (1695 °C) along with a high resistance to cracking.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Hybrid Double Perovskite Containing Helium: [He 2 ][CaZr]F 6

Perovskites are of great technological and geological importance, in large part, due to their considerable compositional and structural flexibility. However, the formation of perovskites with neutral species on their A-sites is very unusual. The formation, phase transitions and properties of [He 2 ][CaZr]F 6 , which is the first noble gas containing perovskite to be made, are reported. It is likely that a large family of related materials can also be prepared. On compression in neon, the negative thermal expansion (NTE) material CaZrF 6 amorphizes at ~ 0. 5 GPa. However, on compression in helium at room temperature, gas is inserted into the structure to form a perovskite with helium on the A-site. This suppresses the amorphization until > 3 GPa. Volume versus pressure and Raman measurements suggest that filling of the A-site, to give [He 2 ][CaZr]F 6 , is complete at > 1 GPa. The presence of helium on the A-site in this perovskite leads to a reduction in the magnitude of negative thermal expansion when compared to the parent phase CaZrF 6 , likely due to steric impediment of the transverse vibrational motion of fluoride. The helium also leads to considerable stiffening of the structure. At room temperature and ~2.5 GPa, the helium containing hybrid perovskite has a bulk modulus of ~ 47 GPa, whereas CaZrF 6 has a bulk modulus of ~ 40 GPa at ambient. At 15 K, the cubic perovskite [He 2 ][CaZr]F 6 undergoes a structural phase transition, that likely involves a cooperative tilting of framework octahedra to give a lower-symmetry phase, which is tentatively assigned as tetragonal.

36 MATERIALS SCIENCE↗
DOE OSTI2022

The Impact of Structural Distortions on the Magnetism of Double Perovskites Containing 5d 1 Transition-Metal Ions

Five double perovskites, each containing a transition-metal ion with a 5d 1 configuration, have been studied to better understand the surprising diversity of magnetic ground states seen in these isoelectronic compounds. Ba 2 ZnReO 6 adopts the cubic double perovskite structure and magnetically orders below 16 K, with a canted ferromagnetic structure and a saturated magnetization of ~0.24 μ B /Re. X-ray magnetic circular dichroism indicates a substantial orbital moment of approximately 0.4 μ B /Re that opposes the spin moment. The structures of Ba 2 NaOsO 6 (canted ferromagnet, T C = 7 K) and Ba 2 LiOsO 6 (antiferromagnet, T N = 8 K) are reinvestigated using time-of-flight neutron powder diffraction and found to crystallize with the cubic double perovskite structure. No evidence for a structural distortion can be found in either compound down to 10 K. Ba 2 CdReO 6 is also cubic at room temperature but undergoes a structural transition upon cooling below ~180 K to a tetragonal structure with I4/m symmetry that involves compression of the Re–O bonds that are parallel to the c-axis. Sr 2 LiOsO 6 shows a similar tetragonal distortion at room temperature and maintains that structure down to 10 K. Surprisingly, the Os-centered octahedron in Sr 2 LiOsO 6 is distorted in the opposite direction, exhibiting an elongation of the Os–O bonds along the c-axis. Differences in the distortions of the octahedra lead to different magnetic ground states, antiferromagnetic (T N = 4 K) for Ba 2 CdReO 6 and spin glass (T g = 30 K) for Sr 2 LiOsO 6 . Theoretical modeling shows that the varied magnetic behaviors of double perovskites containing 5d 1 ions are closely tied to crystallographic distortions. Furthermore, these distortions remove the degeneracy of the 5d t 2g orbitals, leading to changes in orbital occupation that ultimately determine which of the several competing magnetic ground states is favored.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Continuous-Flow Centrifugal Solid/Liquid Separation for the Recovery of Rare-Earth Elements Containing Particles from Phosphoric Acid Sludge

Phosphoric acid sludge contains acid (~54% P 2 O 5 ) and solid precipitates including rare earth elements (REEs) at concentrations of ~2200 ppm. Low-cost recovery of valuable P 2 O 5 and simultaneous solid separation could be an economically feasible approach to recovering REEs while increasing the production of phosphoric acid. The sludge, however, is a complicated stream that cannot be separated by traditional technologies because of high viscosity and a large solid content (30–40%). Guided by a force balance model, an efficient solid/liquid separation method is demonstrated, using a continuous-flow centrifugal contactor. Additionally, the shear regime is bypassed by introducing the sludge directly into the rotor where a centrifugal force is exerted on the fluid, inducing phase separation. Solid particles are trapped in the contactor. High liquid recovery is demonstrated and the effects of process parameters on solid capture are investigated. Three contactors in series yield 94% recovery of solids containing 1500–2895 ppm of REEs.

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

Core-Level Spectroscopy with Hard and Soft X-rays on Phosphorus-Containing Compounds for Energy Conversion and Storage

The electronic properties of nine solid phosphorus (P)-containing compounds with varying oxidation states and chemical environments, including GaP (–III) , InP (–III) , red-P (0) , H 3 P (III) O 3 , Na 2 H 2 P 2 (IV) O 6 , H 3 P (V) O 4 , KH 2 P (V) O 4 , Na 2 HP (V) O 4 , and InP (V) O 4 , are investigated using X-ray absorption near-edge structure (XANES) spectroscopy in the hard (P K-edge) and soft X-ray regime (P L 2,3 - edge). We find shifts in the absorption-edge positions and correlate them with the ligands surrounding the P atom, likely causing a different core–hole interaction screening for different compounds. Complementing the experimental analysis, ab initio many-body calculations of XANES spectra provide insights into the excitonic nature of the observed spectral features and their impact on the electronic structure of the materials. Furthermore, we report on P K-edge XANES measurements on aqueous phosphorus-containing acids, including H 3 PO 3 , H 3 PO 4 , and their mixtures. At first sight, the spectra of the aqueous acids are similar to those of their solid counterparts. However, close inspection reveals a slight red shift of the absorption edge and the presence of fewer spectral features compared with spectra of the respective solids. Mixtures of aqueous acids display spectral features corresponding to the individual components, indicating the potential for speciation and quantification through fingerprinting.

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

Selective Adsorption of Thiol-Containing Molecules on Copper Sulfide Surfaces via Molecule–Surface Disulfide Bridges

Recent results in the fields of nanoenhanced agriculture and expanding interest in prebiotic chemistry have placed increased emphasis on understanding the chemically selective interaction of small molecules with the surfaces of metal sulfides. Here, we present an integrated experimental and computational study of the interaction of thiol-containing molecules with copper sulfide (covellite) surfaces in aqueous media. In situ Fourier-transform infrared (FTIR) measurements and ex situ X-ray photoelectron spectroscopy (XPS) measurements show that molecules bearing free thiol groups, including glutathione and cysteine, bind strongly to CuS (covellite) nanoparticles and to CuS (001) single crystals, while control studies show that similar molecules lacking the free thiol group exhibit much less binding. Additional experiments show that these thiol-containing molecules interact transiently with CuO nanoparticle surfaces but are readily removed by rinsing. The FTIR and XPS experiments demonstrate that adsorption of molecular thiols to CuS surfaces occurs in a chemically selective manner. Further experimental studies and density functional calculations show that the preferred mode of binding is through the surface S atoms, forming a Solid–S–S–Molecule disulfide linkage. While the role of disulfide linkages in controlling structure and function of proteins and other biomolecules is widely known, the formation of surface disulfide linkages as a motif for covalent molecular binding at surfaces has not been established previously.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ion Mobility Spectrometry Characterization of the Intermediate Hydrogen-Containing Gold Cluster Au7(PPh3)7H52+

We employ ion mobility spectrometry and density functional theory to determine the structure of Au7(PPh3)7H52+ (PPh3 = triphenylphosphine) which was recently identified by high mass resolution mass spectrometry. Experimental ion-neutral collision cross sections represent the momentum transfer between the ionic clusters and gas molecules averaged over the relative thermal velocities of the colliding pair, thereby providing structural insights. Theoretical calculations indicate the geometry of Au7(PPh3)7H52+ is similar to Au7(PPh3)7+, with three hydrogen atoms bridging two gold atoms and two hydrogen atoms forming single Au–H bonds. Collision induced dissociation products observed during IMS experiments reveal that smaller hydrogen containing clusters may be produced through fragmentation of Au7(PPh3)7H52+. Our findings indicate that hydrogen containing species like Au7(PPh3)7H52+ act as intermediates in the formation of larger phosphine ligated gold clusters. These results advance the understanding and ability to control the mechanisms of size selective cluster formation which is necessary for scalable synthesis of clusters with tailored properties. This work was supported by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. M.A.H. acknowledges support from the DOE Science Undergraduate Laboratory Internship (SULI) program. H.H. acknowledges support from the DOE Office of Workforce Development for Teachers and Scientist (WDTS) under the Visiting Faculty Program (VFP). The efforts of K.A.M. and B.H.C. were supported by the Defense Threat Reduction Agency (Grant No. HDTRA1-14-1-0023). The research was performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for DOE under Contract DE-AC05-76RL01830.

Ligare, Marshall R.↗
DOE OSTI2024

Physical and Chemical Responses of Amidine-Containing Polymers in the Capture and Release of CO 2

Polymeric materials containing amidine motifs are of high interest due to their ability to reversibly capture and release CO 2 at ambient temperature. Here, in this study, we probe physical and chemical responses of styrene-based copolymers containing linear amidine motifs as functions of CO 2 and inert gas exposures and temperature. A copper-catalyzed azide–alkyne cycloaddition “click” reaction involving N′-propargyl-N,N-dimethylacetamidine is used to modify random copolymers, resulting in an array of linear amidine motifs along the chain backbone with the amount of CO 2 -active amidine controlled by the copolymer composition. Through thermogravimetric measurements, we demonstrate that the amidine-functionalized copolymers efficiently capture CO 2 upon exposure to a stream of CO 2 (at 27 °C) and release it at a slightly elevated temperature (50 °C) when exposed to an inert gas stream (N 2 ). In addition to displaying a maximum adsorption capacity of 22 wt % in the presence of pure CO 2 , the copolymers show composition-dependent direct air capture (DAC) behaviors. Small molecule analogs are used to definitively understand degradation via chemical hydrolysis of the amidine moiety, which leads to insolubility and a large reduction in CO 2 adsorption capacity (1.7 wt %). Neutron vibrational spectroscopy and DFT calculations confirm that CO 2 binds strongly to the amidine motif, inducing a strong bending of the CO 2 molecule from its linear geometry. The coupled insights into mechanisms and behaviors of CO 2 adsorption in amidine-functionalized polymers provides a foundation for future investigations of CO 2 -responsive polymers and soft materials to improve carbon capture and sequestration technologies.

Chun, Danielle J.↗
DOE OSTI2020

Luminescent Properties of DOBDC Containing MOFs: The Role of Free Hydroxyls

A novel metal–organic framework (MOF), Mn-DOBDC, has been synthesized in an effort to investigate the role of both the metal center and presence of free linker hydroxyls on the luminescent properties of DOBDC (2,5-dihydroxyterephthalic acid) containing MOFs. Co-MOF-74, RE-DOBDC (RE–Eu and Tb), and Mn-DOBDC have been synthesized and analyzed by powder X-ray diffraction (PXRD) and the fluorescent properties probed by UV–Vis spectroscopy and density functional theory (DFT). Mn-DOBDC has been synthesized by a new method involving a concurrent facile reflux synthesis and slow crystallization, resulting in yellow single crystals in monoclinic space group C2/c. Mn-DOBDC was further analyzed by single-crystal X-ray diffraction (SCXRD), scanning electron microscopy–energy-dispersive spectroscopy (SEM-EDS), and photoluminescent emission. Results indicate that the luminescent properties of the DOBDC linker are transferred to the three-dimensional structures of both the RE-DOBDC and Mn-DOBDC, which contain free hydroxyls on the linker. In Co-MOF-74 however, luminescence is quenched in the solid state due to binding of the phenolic hydroxyls within the MOF structure. Finally, Mn-DOBDC exhibits a ligand-based tunable emission that can be controlled in solution by the use of different solvents.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Syngas Production at Si Hybrid Photoelectrodes Modified with Re(I) and Mn(I) Tricarbonyl Phenanthroline Complexes Containing Reactive Aryl Azide Groups

We installed molecular CO 2 reduction (CO 2 R) catalysts directly onto Si (photo)electrodes. The highly reactive M(5-azido-1,10-phenanthroline)(CO) 3 X (where M = Mn or Re, X = Br or Cl) complexes readily bubbled when dissolved in polar organic solvents, in both the presence and absence of an ultraviolet light source. When placed on hydrogen-terminated Si (H-Si) and native silicon oxide (SiOx), similar amounts of the complex were attached to the surface under illumination (367 nm, 50–200 mW/cm 2 ) or in the dark. Surprisingly, these films revealed submonolayer coverages instead of the multilayered structures we expected. DFT analyses support monolayer formation, showing that the triplet-state nitrene of the complex is more energetically favorable than the singlet state. Using controlled-potential electrolysis experiments, we showed that Re- and Mn-containing films on pSi photoelectrodes generated small amounts of CO when exposed to 1 atm of CO 2 and 1 sun illumination. These amounts of CO were an order of magnitude greater than control surfaces, producing 5.59 × 10 –7 mol CO/h for Re(az-phen) and 7.83 × 10 –7 mol CO/h for Mn(az-phen) films. Much of the charge passed at the pSi electrodes was consumed by the competing hydrogen evolution reaction, which we attribute to the low molecular coverage and the presence of native oxide on the electrode surface after attachment. Finally, this work demonstrates the feasibility of reacting azide-containing ligands with Si surfaces. Still, it highlights the need for alternative ligand structures and reaction conditions to form multilayer films.

azides↗
DOE OSTI2023

Rigorous Oxidation State Assignments for Supported Ga-Containing Catalysts Using Theory-Informed X-ray Absorption Spectroscopy Signatures from Well-Defined Ga(I) and Ga(III) Compounds

Gallium-based heterogeneous catalysts originally developed for commercial use in propane dehydroaromatization have been explored extensively as potential replacements for Pt- and Cr-based catalysts used in propane dehydrogenation for on-demand propylene production. In a large number of experimental and theoretical studies, active sites with a variety of Ga nuclearities, coordination environments, and oxidation states have been proposed. Isolated Ga(I) ions are often invoked, despite the scarcity of well-defined molecular species and their well-documented instability. In this study, we investigate the appearance of a high-intensity, low-energy white line at the Ga K-edge upon reduction of Ga/HZSM-5 by H 2 at a temperature of ca. 500 °C, accompanied by a dramatic reduction in the extended X-ray absorption fine structure (EXAFS) intensity. In contrast, Ga/γ-Al 2 O 3 does not show such behavior. In order to lay a rigorous foundation for characterizing these types of systems and to establish experimental signatures for the elusive Ga(I) oxidation state, we recorded Ga K-edge X-ray absorption spectra [including high-energy-resolution fluorescence detection-X-ray absorption near-edge spectroscopy (HERFD-XANES)] for several well-defined molecular and crystalline Ga(I) compounds. XANES is essential to establishing the presence of Ga(I), despite the overlap in edge energies with organoGa(III) compounds, because Ga(I)-containing oxide materials show very weak EXAFS scattering. Compared to the XANES of trigonal Ga(III)-containing materials, Ga(I) spectra display a significantly more intense white line feature. Theoretical simulations agree well with this experimental observation and reveal that the strong XANES intensity originates from the superposition of transitions to several empty, nearly degenerate p-like states. Finally, these signatures provide compelling evidence for assigning the intense white line and dramatic loss of EXAFS intensity in Ga/HZSM-5 to the near-quantitative reduction of Ga(III) to Ga(I), while the weaker white line and conventional EXAFS signal of Ga/γ-Al 2 O 3 point to, at most, a minor fraction of Ga(I) sites.

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

Dual Inhibitors of SARS-CoV-2 3CL Protease and Human Cathepsin L Containing Glutamine Isosteres Are Anti-CoV-2 Agents

SARS-CoV-2 3CL protease (Main protease) and human cathepsin L are proteases that play unique roles in the infection of human cells by SARS-CoV-2, the causative agent of COVID-19. Both proteases recognize leucine and other hydrophobic amino acids at the P 2 position of a peptidomimetic inhibitor. At the P 1 position, cathepsin L accepts many amino acid side chains, with a partial preference for phenylalanine, while 3CL-PR protease has a stringent specificity for glutamine or glutamine analogues. We have designed, synthesized, and evaluated peptidomimetic aldehyde dual-target (dual-acting) inhibitors using two peptide scaffolds based on those of two Pfizer 3CL-PR inhibitors, Nirmatrelvir, and PF-835321. Our inhibitors contain glutamine isosteres at the P 1 position, including 2-pyridon-3-yl-alanine, 3-pyridinyl-alanine, and 1,3-oxazo-4-yl-alanine groups. Inhibition constants for these new inhibitors ranged from K i = 0.6–18 nM (cathepsin L) and K i = 2.6–124 nM (3CL-PR), for which inhibitors with the 2-pyridon-3-yl-alanal substituent were the most potent for 3CL-PR. The anti-CoV-2 activity of these inhibitors ranged from EC 50 = 0.47–15 μM. X-ray structures of the peptidomimetic aldehyde inhibitors of 3CL-PR with similar scaffolds all demonstrated the formation of thiohemiacetals with Cys 145 , and hydrogen-bonding interactions with the heteroatoms of the pyridon-3-yl-alanyl group, as well as the nitrogen of the N-terminal indole and its appended carbonyl group at the P 3 position. The absence of these hydrogen bonds for the inhibitors containing the 3-pyridinyl-alanyl and 1,3-oxazo-4-yl-alanyl groups was reflected in the less potent inhibition of the inhibitors with 3CL-PR. In summary, our studies demonstrate the value of a second generation of cysteine protease inhibitors that comprise a single agent that acts on both human cathepsin L and SARS-CoV-2 3CL protease. Such dual-target inhibitors will provide anti-COVID-19 drugs that remain active despite the development of resistance due to mutation of the viral protease. Such dual-target inhibitors are more likely to remain useful therapeutics despite the emergence of inactivating mutations in the viral protease because the human cathepsin L will not develop resistance. This particular dual-target approach is innovative since one of the targets is viral (3CL-PR) required for viral protein maturation and the other is human (hCatL) which enables viral infection.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Spray Mechanism of Contained-Electrospray Ionization

Analytical characteristics of contained electrospray ionization (ESI) are summarized in terms of its potential to modify the analyte solution during the stages of droplet formation to provide opportunities to generate native versus denatured biomolecular gas-phase ions, without the need for bulk-phase analyte modifications. The real-time modification of the charged microdroplets occurs in a cavity that is included in the outlet of the contained-ESI ion source. Close examination of the inside of the cavity using a high-speed camera revealed the formation of discrete droplets as well as thin liquid films in the droplets wake. When operated at 20 psi N2 pressure, the droplets were observed to move at an average speed of 8 mm/s providing ~1 s mixing time in a 10 mm cavity length. Evidence is provided for the presence of highly reactive charged droplets based on myoglobin charge state distribution, apo-myoglobin contents, and ion mobility drift time profiles under different spray conditions. Mechanistic insights for the capture of vapor-phase reagents and droplet dynamics as influenced by different operational modes are also described.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Liquid Containing Clouds at the North Slope of Alaska Demonstrate Sensitivity to Local Industrial Aerosol Emissions

Abstract Cloud condensation nucleus control alter cloud solar albedo through cloud droplet size. Here, we leverage anthropogenic emissions at the North Slope of Alaska as a natural laboratory to study relationships between aerosols and Arctic liquid‐containing clouds. Averaging 14 years of MODIS observations, we found a reduction in temporally averaged cloud effective radius ( ) of up to 1.0 μm related to localized pollution. Pronounced regional gradients in cloud frequency of occurrence and liquid water path prohibit the detection of potential changes of these variables. Observed changes of alter radiative fluxes and increase cloud‐reflected shortwave radiation by up to 0.8 W m − 2 in the Prudhoe Bay area for the period covered by observations (April–September). Due to the frequent occurrence of liquid‐containing clouds, this implies that enhanced local emissions in Arctic regions can impact climate processes.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Calendar aging of silicon-containing batteries

High-energy batteries for automotive applications require cells to endure well over a decade of constant use, making their long-term stability paramount. This is particularly challenging for emerging cell chemistries containing silicon, for which extended testing information is scarce. While much of the research on silicon anodes has focused on mitigating the consequences of volume changes during cycling, comparatively little is known about the time-dependent degradation of silicon-containing batteries. Here we discuss a series of studies on the reactivity of silicon that, collectively, paint a picture of how the chemistry of silicon exacerbates the calendar aging of lithium-ion cells. Assessing and mitigating this shortcoming should be the focus of future research to fully realize the advantages of this battery technology.

25 ENERGY STORAGE↗
DOE OSTI2020

Molecular growth upon ionization of van der Waals clusters containing HCCH and HCN is a pathway to prebiotic molecules

The growth mechanisms of organic molecules in an ionizing environment such as the interstellar medium are not completely understood. Here we examine by means of ab initio molecular dynamics (AIMD) simulations and density functional theory (DFT) computations the possibility of bond formation and molecular growth upon ionization of van der Waals clusters of pure HCN clusters, and mixed clusters of HCN and HCCH, both of which are widespread in the interstellar medium. Ionization of van der Waals clusters can potentially lead to growth in low temperature and low-density environments. Our results show, that upon ionization of the pure HCN clusters, strongly bound stable structures are formed that contain N∙∙∙H bonds, and growth beyond pairwise HCN molecules is seen only in a small percentage of cases. In contrast, mixed clusters, where HCCH is preferentially ionized over HCN, can grow up to 3 or 4 units long with new carbon–carbon and carbon–nitrogen covalent bonds. Moreover, cyclic molecules formed, such as the radical cation of pyridine, which is a prebiotic molecule. The results presented here are significant as they provide a feasible pathway for molecular growth of small organic molecules containing both carbon and nitrogen in cold and relatively denser environments such as in dense molecular clouds but closer to the photo-dissociation regions, and protoplanetary disks. In the mechanism we propose, first, a neutral van der Waals cluster is formed. Once the cluster is formed it can undergo photoionization which leads to chemical reactivity without any reaction barrier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Thiol-promoted catalytic synthesis of high-performance furan-containing lubricant base oils from biomass derived 2-alkylfurans and ketones

About 97% of lubricant base oils are currently sourced from petroleum and the majority of the rest is produced from vegetable oils. We demonstrate a promising catalytic route to produce base oils from lignocellulosic biomass-derived 2-alkylfurans and ketones via carbon–carbon coupling in neat conditions. Among several homogeneous and heterogeneous acid catalysts tested, a perfluorinated sulfonic acid (Aquivion PW79S) exhibits the best catalytic performance and yields up to 90% renewable furan-containing base oils with the use of a thiol promotor. The effects of the acid strength of the catalysts, molecular size and structure of thiols and ketones, and fraction of thiols are studied. Electronic structure calculations elucidate the reaction pathway and indicate that the thiol reduces the barrier of the rate-determining dehydration step. The structure and properties of base oils can be tuned by using different synthons. Here, these base oils have excellent properties and can be competitive with or surpass the commercial synthetic alkylnaphthalene and furan-containing bio-ester base oils.

09 BIOMASS FUELS↗
DOE OSTI2023

Investigation of a bacteriochlorin-containing pentad array for panchromatic light-harvesting and charge separation

A new pentad array designed to exhibit panchromatic absorption and charge separation has been synthesized and characterized. The array is composed of a triad panchromatic absorber (a bis(perylene-monoimide)-porphyrin) to which are appended an electron acceptor (perylene-diimide) and an electron donor/hole acceptor (bacteriochlorin) in a crossbar arrangement. The motivation for incorporation of the bacteriochlorin versus a free-base or zinc chlorin utilized in prior constructs was to facilitate hole transfer to this terminal unit and thereby achieve a higher yield of charge separation across the array. The intense S 0 → S 1 (Q y ) band of the bacteriochlorin also enhances absorption in the near-infrared spectral region. Due to synthetic constraints, a phenylethyne linker was used to join the bacteriochlorin to the core porphyrin of the panchromatic triad rather than the diphenylethyne linker employed for the prior chlorin-containing pentads. Static and time-resolved photophysical studies reveal enhanced excited-state quenching for the pentad in benzonitrile and dimethyl sulfoxide compared to the prior chlorin-containing analogues. Success was only partial, however, as a long-lived charge separated state was not observed despite the improved energetics for the final ground-state hole/electron-shift reaction. The apparent reason is more facile competing charge-recombination due to the shorter bacteriochlorin – porphyrin linker that increases electronic coupling for this process. Furthermore, the studies highlight design criteria for balancing panchromatic absorption and long-lived charge separation in molecular architectures for solar-energy conversion.

14 SOLAR ENERGY↗