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NASA NTRS1990

Molten (Mg0.88Fe0.12)2SiO4 at lower mantle conditions - Melting products and structure of quenched glasses

Infrared spectra of quenched magnesium silicate glasses synthesized by fusing olivine at pressures in excess of 50 GPa and temperatures greater than 2500 K demonstrate that silicon is dominantly present in four-fold coordination with respect to oxygen within these quenched glasses. This low coordination is attributed, by analogy with the structural behavior of glasses compressed at 300 K, to the instability of higher coordinations in glasses of these compositions on decompression. Spectra of glasses formed in a hydrous environment document that water is extensively soluble in melts at these high pressures and temperatures. Also, these results are consistent with the melting of (Mg0.88Fe0.12)2SiO4 compositions to liquids near pyroxene in stoichiometry under these conditions, with iron-rich magnesiowuestite being the liquidus phase.

Williams, Quentin↗

DOE OSTI2023

Diesel fuel properties of renewable polyoxymethylene ethers with structural diversity

Polyoxymethylene ethers (POMEs) are a class of low-soot and high-cetane oxygenate oligomers of structure RO-(CH 2 O-) $n$ -R, with different chain lengths ($n$) and end-groups (R) that determine their diesel-like fuel properties. Commercial POMEs with methyl end-groups (MM-POME 3-6 ) exhibit undesirably low energy density and high-water solubility. A previous computational assessment indicated that the lower heating value (LHV) and water solubility for MM-POME 3-6 both improve upon end-group exchange with larger butyl, $iso$-butyl and $iso$-pentyl end-groups. Here, we expanded upon our initial trans-acetalization reaction that employed 1-butanol to install butyl end-groups to also include branched, higher carbon-number end-groups using $iso$-butanol and fusel oil as reagents. Additionally, these new products are termed $i$B*POME 1-6 , and FOil*POME 1-5 , respectively, and collectively referred to as R*POMEs. They possess the advantaged properties of the parent MM-POME 3-6 while exhibiting higher LHV (31 MJ kg -1 and 28 MJ kg -1 for $i$B*POME 1-6 , and FOil*POME 1-5 , respectively) and much reduced water solubility (2.7 g L -1 and 1 g L -1 for $i$B*POME 1-6 , and FOil*POME 1-5 , respectively). Additional fuel property analyses were performed using 20 vol% blends of the R*POMEs with a base diesel fuel. Overall, the greater energy density and decreased water solubility of the R*POMEs, as well as their synergistic blending with diesel at moderate blend levels, provide the greatest benefits to consumers and position this group of products as an environmentally friendlier blendstock alternative to the commercially available MM-POME 3-6 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2008

Diversity and Physiology of Siderophilic Cyanobacteria: Implication for the Bioenergetics

Prior to 2.4 Ga, global oceans were likely significantly enriched in soluble iron (Rouxel, Bekker, Edwards, 2005), a condition that is not conducive to the growth of most contemporary mesophilic cyanobacteria (CB). Recent studies of the mechanisms of iron-deficiency stress in CB suggest that contemporary mesophilic freshwater and marine B underwent long-term adaptation to a permanent decrease in soluble iron in the ocean environment (Boyer, et al., 1987; Braun, Hantke, and Koster, 1998). Of all extant environments, iron-depositing hot springs may constitute the most appropriate natural models for analysis of the transition of ancestral cyanobacteria (CB) or protocyanobacteria (PCB) (Olson, 2001) from anoxygenic photosynthesis to oxygenic one and biogeochemical processes in the late Archean and early Paleoproterozoic eras. In particular, Olson (2001) proposed the definition for PCB and postulated that the common ancestor of PCB and CB might well have used Fe(OH)+ as the principal electron donor for CO2 fixation (Widdel, et al., 1993; Ehrenreich and Widdel, 1994; Pierson and Olson, 1989; Olson, 2006). Olson (2001) proposed that the driving force for the evolution of RC2, in addition to RC1, was the necessity to use Fe(OH)+ effectively for CO2 fixation in the absence of reduced sulfur compounds. The global decrease of dissolved environmental reduced iron could have been the driving force for the transition from anoxygenic to oxygenic photosynthesis (Brown et al., 2007). Despite the insights into the ecology, evolutionary biology, paleogeobiochemistry, and astrobiology the examination of iron depositing hot springs (IDHS) could potentially provide, very few studies dedicated to the diversity and physiology of cyanobacteria inhabiting IDHS have been conducted. Here we describe the phylogeny, physiology and ultrastructure and biogeochemical activity of several recent CB isolates from two different greater Yellowstone area IDHS, e.g. LaDuke and Chocolate Pots. Phylogenetic analysis of 16S rRNA genes indicated that 6 of 12 new isolates examined could not be placed within established CB genera. Some of the isolates exhibited pronounced requirements for elevated iron concentrations, with maximum growth rates observed when 0.4-1 mM Fe(3+) was present in the media. However, the pronounced effect of iron limitation on the proliferation of siderophilic CB can be observed only after several passages through iron "free" media. TEM studies of several species of siderophilic CB revealed that the cultures JSC-3 and -11 are probably capable of some sort of pinocytosis of precipitated iron. This phenomenon may explain high tolerance of siderophilic CB to iron deficit. We also found that the stimulation of the growth of siderophilic CB by oxidized iron is accompanied by the decrease of O2 evolution by some species after addition Fe(2+) in iron "free" medium.

Brown, Igor↗

DOE OSTI2025

Impacts of Precipitation Events on Concentrations of Oxygenated Gas- and Particle-Phase Compounds Observed in the Amazon

Removal of gases and particles by precipitation (wet deposition) is a critical process that significantly influences the transport and chemical transformation of atmospheric compounds. However, there are few studies that directly measure or constrain the rates of this process under real-world conditions. This work quantifies the net change in ambient concentrations during precipitation events (removal rates) of gas- and particle-phase organic compounds at a surface site near Manaus, Brazil, during the GoAmazon2014/5 campaign. Removal rates of identified and unknown compounds that have been previously classified into source-based clusters are measured during rain events and categorized based on estimated properties of compounds and clusters. Highly oxygenated gases, such as isoprene oxidation products, are removed during precipitation events with a median removal rate of 0.09 h –1 and the fastest analyte is removed at a rate of 0.22 h –1 . Removal rates of particle-phase compounds are observed at roughly this median rate, while less soluble gases, such as terpenes, exhibit low removal rates. These results are roughly in agreement with prior theoretical estimates of wet deposition rates for comparable compounds, providing an empirical point of comparison while noting that our metric reflects the net influence of precipitation events rather than wet deposition alone.

atmospheric chemistry↗

DOE OSTI2022

Utilization of lignocellulosic biofuel conversion residue by diverse microorganisms

Lignocellulosic conversion residue (LCR) is the material remaining after deconstructed lignocellulosic biomass is subjected to microbial fermentation and treated to remove the biofuel. Technoeconomic analyses of biofuel refineries have shown that further microbial processing of this LCR into other bioproducts may help offset the costs of biofuel generation. Identifying organisms able to metabolize LCR is an important first step for harnessing the full chemical and economic potential of this material. In this study, we investigated the aerobic LCR utilization capabilities of 71 Streptomyces and 163 yeast species that could be engineered to produce valuable bioproducts. The LCR utilization by these individual microbes was compared to that of an aerobic mixed microbial consortium derived from a wastewater treatment plant as representative of a consortium with the highest potential for degrading the LCR components and a source of genetic material for future engineering efforts. We analyzed several batches of a model LCR by chemical oxygen demand (COD) and chromatography-based assays and determined that the major components of LCR were oligomeric and monomeric sugars and other organic compounds. Many of the Streptomyces and yeast species tested were able to grow in LCR, with some individual microbes capable of utilizing over 40% of the soluble COD. For comparison, the maximum total soluble COD utilized by the mixed microbial consortium was about 70%. This represents an upper limit on how much of the LCR could be valorized by engineered Streptomyces or yeasts into bioproducts. To investigate the utilization of specific components in LCR and have a defined media for future experiments, we developed a synthetic conversion residue (SynCR) to mimic our model LCR and used it to show lignocellulose-derived inhibitors (LDIs) had little effect on the ability of the Streptomyces species to metabolize SynCR. We found that LCR is rich in carbon sources for microbial utilization and has vitamins, minerals, amino acids and other trace metabolites necessary to support growth. Testing diverse collections of Streptomyces and yeast species confirmed that these microorganisms were capable of growth on LCR and revealed a phylogenetic correlation between those able to best utilize LCR. Identification and quantification of the components of LCR enabled us to develop a synthetic LCR (SynCR) that will be a useful tool for examining how individual components of LCR contribute to microbial growth and as a substrate for future engineering efforts to use these microorganisms to generate valuable bioproducts.

09 BIOMASS FUELS↗

NASA NTRS2013

Possible Detection of Perchlorates by the Sample Analysis at Mars (SAM) Instrument: Comparison with Previous Missions

The first chemical analysis of soluble salts in the soil was carried out by the Phoenix Lander in the Martian Arctic [1]. Surprisingly, chlorine was present as magnesium or calcium perchlorate at 0.4 to 0.6 percent. Additional support for the identification of perchlorate came from the evolved gas analysis which detected the release of molecular oxygen at 350-550C [1]. When Mars-like soils from the Atacama Desert were spiked with magnesium perchlorate (1 percent) and heated using the Viking GC-MS protocol, nearly all the organics were combusted but a small amount was chlorinated, forming chloromethane and dichloromethane [2]. These chlorohydrocarbons were detected by the Viking GC-MS experiments when the Martian soil was analyzed but they were considered to be terrestrial contaminants [3]. Reinterpretation of the Viking results suggests <0.1 percent perchlorate and ppm levels of organic carbon at landing site 1 and 2 [2]. The suggestion of perchlorate in the Viking sites [2] has been challenged on the grounds that the detected compounds (CH3Cl and CH2Cl2) were carried from Earth [4]. Recently the Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory (MSL) ran four samples from an aeolian bedform named Rocknest. The samples analyzed were portioned from the fifth scoop at this location. The samples were heated to 835C at 35C/min with a He flow. The SAM QMS detected a major oxygen release (300-500C) [5], coupled with the release of chlorinated hydrocarbons (chloromethane, dichloromethane, trichloromethane, and chloromethylpropene) detected both by SAM QMS and GC-MS derived from known Earth organic contaminants in the instrument [6]. Calcium perchlorate appears to be the best candidate for evolved O2 in the Rocknest samples at this time but other Cl species (e.g., chlorates) are possible and must be evaluated. The potential detection of perchlorates in Rocknest material adds weight to the argument that both Viking Landers measured signatures of perchlorates. Even if the source of the organic carbon detected is still unknown, the chlorine source was likely Martian. Two mechanisms have been hypothesized for the formation of soil perchlorate: (1) Atmospheric oxidation of chlorine; and (2) UV photooxidation of chlorides catalyzed by mineral catalysts [7]. The presence of soil perchlorates in the Martian surface has important implications for the detection of organics [2], carbonates [8] and nitrates [9] by SAM.

Navarro-Gonzalex, Rafael↗

NASA NTRS2017

Redox Variations in Early Solar System Materials and Implications for Late Stage Planetary Accretion and Planet Formation

Oxygen fugacity plays an important role in determining the detailed physical and chemical aspects of planets and their building blocks. Basic chemical properties such as the amount of oxidized Fe in a mantle (as FeO), the nature of alloying elements in the core (S, C, H, O, Si), and the solubility of various volatile elements in the silicate and metallic portions of embryos and planets can influence physical properties such as the size of the core, the liquidus and solidus of the mantle and core, and the speciation of volatile compounds contributing to atmospheres. This paper will provide an overview of the range of fO2 variation observed in primitive and differentiated materials that may have participated in accretion (cosmic dust, Star-dust and meteorites), a comparison to observations of planetary fO2 (Mercury, Mars and Earth), and a discus-sion of timing of variation of fO2 within both early and later accreted materials. This overview is meant to promote discussion and interaction between students of these two stages of planet formation to identify areas where more work is needed.

Righter, K.↗

NASA NTRSDate not supplied

Effect of Tungsten L-PBF Feedstock Modification on Performance in Bending

Additively manufactured tungsten is a candidate refractory material for high-temperature aerospace and nuclear fusion/fission applications. The printability of pure tungsten is challenged by cracking defects arising from the metal’s high ductile-to-brittle transition temperature and low solubility of interstitial impurities. Furthermore, the cast microstructure inherent to the laser powder bed fusion (L-PBF) process has limited strength compared to worked microstructures common in wrought tungsten. Aside from process-related techniques to mitigate defects and increase strength (e.g., heated build chambers, multi-laser systems, low oxygen environmental control, etc.), micro-alloying additions can positively influence tungsten printability. In this work, pure tungsten L-PBF feedstock was modified with 1 wt% additions of ceramic compound nano-powders. Wrought and printed bars were evaluated in four-point bending. Flexural strength and fractography were primary means of comparison to assess the effect of the feedstock modification on printed tungsten mechanical performance.

Tungsten-based alloys↗

NASA NTRS2024

Bending Performance of Tungsten Printed Via Laser Powder Bed Fusion With Ceramic Dispersion Modified Powder Feedstock

Additively manufactured tungsten is a candidate refractory material for high-temperature aerospace and nuclear fusion/fission applications. The printability of pure tungsten is challenged by cracking defects arising from the metal’s high brittle-to-ductile transition temperature and low solubility of interstitial impurities. Furthermore, the cast microstructure inherent to the laser powder bed fusion (L-PBF) process has limited strength compared to worked microstructures common in wrought tungsten. Aside from process-related techniques to mitigate defects and increase strength (e.g., heated build chambers, multi-laser systems, low oxygen environmental control, etc.), micro-alloying additions can positively influence tungsten printability and strength. In this work, pure tungsten L-PBF feedstock was modified with 1 wt% additions of ceramic compound nano-powders. Wrought and printed bars were evaluated in four-point bending. Flexural strength and fractography were primary means of comparison to assess the effect of the feedstock modification on printed tungsten mechanical performance.

Additive Manufacturing↗

DOE OSTI2019

Krypton storage capacity of the Earth's lower mantle

Noble gases are important geochemical tracers allowing reconstructing global volatile cycles in Earth's reservoirs. To constrain these fundamental processes, precise data on their partitioning behavior at deep Earth conditions are needed. Such data are only available at moderate pressures up to 25 GPa due to experimental challenges. We have investigated the possibility of noble gas storage in the Earth's lower mantle up to 115 GPa. We studied the incorporation of krypton in the second most abundant lower mantle mineral (Mg 1-x ,Fe x )O (ferropericlase) as well as in liquid metal-alloys by performing experiments up to 115 GPa and 3700 K using the laser-heated diamond anvil cell coupled to post-mortem EMPA analysis and X-ray absorption spectroscopy. The results reveal that, at these extreme conditions, up to 3 wt.% of krypton can be stored in (Mg 1-x ,Fe x )O and 3000 ppm in the Fe-rich liquid metal. For both phases the storage capacities increase with pressure (between 40 GPa and 60 GPa) at a constant high temperature of 2300 K. Fpc has never been considered as a NG host, despite being the second most abundant mineral in the Earth's LM. Using recent accurate compressibility data, we demonstrate that a substitution of krypton into the anion site of (Mg 1-x ,Fe x )O in form of neutral oxygen Schottky defects at diluted lower mantle conditions is possible. This noble gas incorporation mechanism is in agreement with a previous study on bridgmanite. We show that (Mg 1-x ,Fe x )O exhibits higher noble gas storage capacities than bridgmanite through the lower mantle using lattice strain modeling and including experimental solubility and thermoelastic data for neon, argon, krypton and xenon. We also demonstrate that both phases exhibit the highest solubilities for argon and krypton. We used the solubility data from lattice strain modeling to predict noble gas abundances stored in the solid lower mantle after magma ocean crystallization. The modeled abundances show apparent similarities with estimates for the deep noble gas reservoir that are based on either 3He abundances in ocean island basalts or radiogenic 40Ar abundances in the bulk Earth. This strongly indicates that the crystalline lower mantle may play an important role as deep noble gas storage reservoir. We propose, based on considerations on noble gas replenishment from the lower mantle to the atmosphere, that the lower mantle can only contribute to a small fraction of the present-day atmospheric noble gases. This suggests that the lower mantle is an un-degassed reservoir.

58 GEOSCIENCES↗

DOE OSTI2021

Use of a Lewis acid, a Brønsted acid, and their binary mixtures for the hydrothermal liquefaction of lignocellulose

The main objective of the present study is to investigate the effect of a Lewis acid, Brønsted acid, and their combined use on the hydrothermal liquefaction of lignocellulosic biomass. Hydrothermal liquefaction of teak wood was conducted at 250, 300 and 350 °C for 15, 30 and 60 min. Hydrothermal liquefaction of teak wood was carried out at 300 °C for 30 min (the best optimum conditions) without and with the use of Mg(ClO 4 ) 2 , HClO 4 , and HClO 4 /Mg(ClO 4 ) 2 at various loadings (2–10 mmol/15 g wood). The highest bio-oil yield was obtained with the non-catalytic run. All tested catalysts have negative effect on bio-oil yields. The bio-oil yields generally decreased with increasing the catalyst loadings. The deoxygenation degree in bio-oils changed depending on the type of catalyst and loading. A high degree of de-oxygenation took place with Mg(ClO 4 ) 2 catalysts. An increased catalyst loading led to decreased aromatic contents of bio-oils catalyzed by either Mg(ClO 4 ) 2 or HClO 4 . The use of a catalyst increased total naphtha fractions in bio-oils. The highest heating value of the bio-oil was estimated to be approximately 30 MJ/kg. Gas chromatography–mass spectrometry analysis revealed that the bio-oils from the non-catalytic and catalytic runs contained aldehydes, ketones, phenols, acids, esters and alcohols. Furthermore, the relative yields of the oxygenated compounds were affected by catalyst type.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1981

Benzoic acid degradation of polyacrylonitrile fibers

The reactions of polyacrylonitrile (PAN) fibers in the presence of benzoic acid have been studied. Polyacrylonitrile fibers oxidize more readily in the presence of benzoic acid than in air at temperatures in the range of 170 C. The product decreased in solubility with extent of reaction. Gel permeation chromatography of the soluble fraction showed change in polydispersity. The insoluble product exhibited differences in weight loss as a function of decomposition temperature compared to PAN fibers. Infrared analyses of the fiber product showed absorption peaks similar to air-oxidized PAN. High-energy photoelectron spectral analysis showed a carbon-rich surface which contained oxygen and nitrogen. An air oxidized sample of fiber contained more oxygen at the surface than a fiber treated first with benzoic acid and then air oxidized.

Varma, D. S.↗

NASA NTRS1981

Benzoic acid degradation of polyacrylonitrile fibers

Varma, D. S.↗

DOE OSTI2022

Phenyl‐Free Polynorbornenes for Potential Anion Exchange Ionomers for Fuel Cells and Electrolyzers

Abstract Ionomers in the catalyst layer play a critical role in the performance of fuel cells and electrolyzers. Phenyl adsorption on hydrogen oxidation catalysts and electrochemical oxidation of phenyl moieties on oxygen evolution catalysts are detrimental to the alkaline devices’ performance. Here the adsorption energy of phenyl‐containing ionomers is compared to provide the rationale for implementing phenyl‐free ionomers. Density functional theory calculations indicated that the norbornane fragment has minimal adsorption energy on Pt(111) due to the absence of aromatic π electrons. A soluble quaternized polynorbornene ionomer is prepared by vinyl addition polymerization, and it exhibits high performance in both fuel cells and electrolyzers, proving the advantage of the phenyl‐free structure. This study establishes the phenyl adsorption energy‐electrode performance relationship, highlighting the importance of material interactions between the catalysts and ionomers.

25 ENERGY STORAGE↗

DOE OSTI2024

Unveiling the nucleation and growth of Zr oxide precipitates in internally oxidized Nb3Sn superconductors

We report on atomic-scale analyses of nucleation and growth of Zr oxide precipitates and the microstructural evolution of internally oxidized Nb3Sn wires for high-field superconducting magnet applications, utilizing atom probe tomography (APT), transmission electron microscopy (TEM), and first-principles calculations. APT analyses reveal that oxygen and zirconium are already segregated at grain boundaries (GBs) in the unreacted Nb-1Zr-4Ta (at%) alloy prior to forming Nb3Sn through reacting the Nb alloy with Sn and SnO2. After forming Nb3Sn, Zr oxide precipitates nucleate both at the Nb3Sn/Nb heterophase interfaces and in the Nb3Sn grains, driven by the small solubilities of Zr and O in Nb3Sn compared to their value in Nb. A high number density (Nv) of Zr oxide nanoprecipitates is observed in the Nb3Sn layers, ∼10 23 m −3 , with a mean diameter <10 nm for a heat treatment at 625 °C. Quantitative APT and TEM analyses of the Zr oxide precipitates in the reacted Nb3Sn layers elucidate details of the nucleation, growth, and coarsening processes of the Zr oxide precipitates in Nb3Sn. First-principles calculations and classical nucleation theory are employed to study the nucleation of Zr oxide precipitates in Nb3Sn and to estimate the maximum energy barrier and critical radius for nucleation. Our research unveils the kinetic pathways for nucleation and growth of Zr oxide precipitates and the microstructural evolution of Nb3Sn layers, which helps to understand and improve the superconducting properties of internally oxidized Nb3Sn wires for use in high-field superconducting magnets. •We investigated the nucleation and growth of Zr oxide nanoprecipitates in Nb3Sn superconductors for magnet applications.•APT and TEM analyses reveals the nucleation and growth process of Zr oxide precipitates in Nb3Sn layers.•Classical nucleation theory with DFT is employed to describe the nucleation process of Zr oxide precipitates in Nb3Sn.•We find that the interfacial reactions at Nb/Nb3Sn interface play a critical role in the nucleation of Zr oxide precipitates.•Current study provides a pathway to improve the properties of internally oxidized Nb3Sn superconducting wires.

43 PARTICLE ACCELERATORS↗

NASA NTRS2004

Lithium Polymer Electrolytes and Solid State NMR

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Berkeley, Emily R.↗

DOE OSTI2020

Non-catalytic oxidative depolymerization of lignin in perfluorodecalin to produce phenolic monomers

We demonstrate for the first time non-catalytic, oxidative cracking with molecular oxygen (O 2 ) to depolymerize native lignin into oxygenated phenolic monomers. Maximum monomer yield of 10.5 wt% was achieved at 250 °C after only 10 min of reaction and included vanillin, syringaldehyde, vanillic acid, and syringic acid. High rates of oxidation are attributed to the use of perfluorodecalin as solvent. Perfluorodecalin is a perfluorocarbon (PFC), characterized by their chemical stability and exceptionally high solubility for O 2 . Monomer yields were typically five-fold higher in perfluorodecalin compared to solvents more commonly employed in lignin conversion, such as methanol, butanol, acetonitrile, and ethyl acetate. Phenolic monomer production in perfluorodecalin favors high temperatures and short reaction times to prevent further oxidation of the produced monomers. Lignin oil obtained under oxidative conditions in perfluorodecalin showed lower molecular weight and smaller polydispersity compared to other solvents. Increasing the reaction time further decreased the molecular weight, while increasing reaction time in an inert atmosphere increased the molecular weight of the lignin oil. High concentrations of O 2 in perfluorodecalin not only increased lignin depolymerization but suppressed undesirable condensation reactions. Depolymerization is likely initiated by thermally induced homolytic cleavage of ether linkages in lignin to form phenoxy and carbon-based radicals. These radicals bind with O 2 as a radical scavenger and further react to form phenolic monomeric products rather than repolymerizing to large oligomers. The PFC process was scaled from 5 mL to 250 mL without any loss of yield. Because most organic compounds are not soluble in perfluorodecalin, recycling is easily achieved via liquid–liquid separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

meso -Ethynyl-extended push–pull type porphyrins for near-infrared organic photodetectors

We report natural porphyrins play a key role in a range of vital functions such as oxygen transport in the bloodstream and the conversion of light to chemical energy in plants. Likewise, synthetic porphyrin derivatives can be used to detect light and convert it into an electrical current in photodiodes. The versatility of porphyrinoid chemistry allows to extend the absorptivity (and hence detectivity) to the near-infrared while maintaining good solubility, suitable electrochemical properties, and compatibility with the electron acceptor molecules required to achieve a reasonable photocurrent. Here, our efforts on the design and synthesis of novel push–pull type meso-ethynyl-extended porphyrin compounds, both of A–D–A and D–A–D type (D = donor, A = acceptor), and their evaluation in prototype near-infrared organic photodetector devices are presented. The push–pull design with strongly electron-deficient building blocks results in absorption onsets up to 1200 nm, translating in an optical gap approaching 1 eV. Both A–D–A and D–A–D small molecules show good photodetector performance, with a peak specific detectivity near 2 x 10 11 and 4 x 10 11 Jones at 1000 nm (at -2 V bias), respectively. These values are among the best reported so far for small molecule based near-infrared organic photodetectors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗