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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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Antimicrobial Properties of Corn Stover Lignin Fractions Derived from Catalytic Transfer Hydrogenolysis in Supercritical Ethanol with a Ru/C Catalyst
Converting lignin to value-added products at high yields provides an avenue for making ethanol biorefineries more profitable while reducing the carbon footprint of products generally derived from petroleum. In this study, corn stover lignin was depolymerized by catalytic transfer hydrogenolysis (CTH) in supercritical ethanol with a Ru/C catalyst. The lignin-derived bio-oil was then sequentially extracted utilizing hexane, petroleum ether, chloroform, and ethyl acetate as solvents in order of less polar to polar, and the subsequent bio-oils were characterized using GPC, GC/MS, and HSQC NMR. In this work, results show that the monomers in the bio-oil fractions contained primarily alkylated phenols, hydrogenated hydroxycinnamic acid derivatives, syringol and guaiacol-type lignins created from reductive cleavages of ether linkages, which were sequentially extracted into groups depending on the solvent polarity. The antimicrobial properties of the bio-oils were screened against Gram-positive (Bacillus subtilis, Lactobacillus amylovorus, and Staphylococcus epidermidis) and Gram-negative (Escherichia coli) bacteria and yeast (Saccharomyces cerevisiae) by examining microbial growth inhibition. Results show that CTH-derived bio-oils inhibited all tested organisms at concentrations less than 3 mg/mL. Total monomer concentration and the presence of specific monomers (i.e., syringyl propane) showed correlations to antimicrobial activity, likely due to cell death or membrane damage. This study provides insights into using sequential extraction to fractionate lignin-derived compounds and correlations between the properties of the extracted compounds and their antimicrobial activity.
Production of a δ-Lactam from Glucose through Integrating Biological and Chemical Catalysis
We present a new strategy for the production of a δ-lactam from glucose that integrates biological production of triacetic acid lactone (TAL, 4-hydroxy-6-methyl-2H-2-one) with catalytic transformation of TAL into 6-methylpiperidin-2-one (MPO) through metabolic engineering, isomerization, amination, and catalytic hydrogenation/hydrogenolysis. We developed a sustainable and antibiotic-free fed-batch fermentation using genetically modified Rhodotorula toruloides IFO0880. This process achieved a yield of 2-hydroxy-6-methyl-4H-pyran-4-one (2H4P) at 0.05 g/g of glucose, corresponding to a 9.9 g/L titer. By adjusting the pH of the fermentation broth to 2, 2H4P was quantitatively converted into TAL. The TAL in the fermentation broth was directly converted by aminolysis into 4-hydroxy-6-methylpyridin-2(1H)-one (HMPO), which achieved an 18.5% yield with 94.3% purity. The HMPO yield was lower in the fermentation broth than in a clean feedstock (32.2%), suggesting that the biological impurities are inhibitors in this reaction. Further investigation revealed that lower pH levels and reduced TAL concentrations in the fermentation broth significantly decreased HMPO yields. Subsequently, the precipitated HMPO was filtered and dried and then subjected to the final catalytic conversion in H2O solvent, achieving a MPO yield of 91.8%. Furthermore, this integrated approach demonstrated the direct use of TAL in the filtered aqueous fermentation broth without the need to isolate TAL.
Compartmentalization and Photo-Regulating Pathways for Incompatible Tandem Catalysis
This contribution describes an advanced compartmentalized micellar nanoreactor that possesses a reversible photoresponsive feature and its application towards photo-regulating reaction pathways for incompatible tandem catalysis under aqueous conditions. The smart nanoreactor is based on multi-functional amphiphilic poly(2-oxazoline)s and covalently crosslinked with spiropyran upon micelle formation in water. It responds to light irradiation in a wavelength-selective manner switching its morphology as confirmed by dynamic light scattering and cryo-transition electron microscopy. The compartmental structure renders distinct nanoconfinements for two incompatible enantioselective transformations: a rhodium-diene complex-catalyzed asymmetric 1,4-addition occurs in the hydrophilic corona while a Rh-TsDPEN-catalyzed asymmetric transfer hydrogenation proceeds in the hydrophobic core. Control experiments and kinetic studies showed that the gated behavior induced by the photo-triggered reversible spiropyran to merocyanine transition in the cross-linking layer is key to discriminate among substrates/reagents during the catalysis. Here, the smart nanoreactor realized photo-regulation to direct the reaction pathway to give a multi-chiral product with high conversions and perfect enantioselectivities in aqueous media. Our SCM catalytic system, on a basic level, mimics the concepts of compartmentalization and responsiveness Nature uses to coordinate thousands of incompatible chemical transformations into streamlined metabolic processes.
Pendent Relay Enhances H 2 O 2 Selectivity during Dioxygen Reduction Mediated by Bipyridine-Based Co–N 2 O 2 Complexes
Generally, cobalt–N 2 O 2 complexes show selectivity for hydrogen peroxide during electrochemical dioxygen (O 2 ) reduction. We recently reported a Co(III)–N 2 O 2 complex with a 2,2'-bipyridine-based ligand backbone which showed alternative selectivity: H 2 O was observed as the primary reduction product from O 2 (71 ± 5%) with decamethylferrocene as a chemical reductant and acetic acid as a proton donor in methanol solution. We hypothesized that the key selectivity difference in this case arises in part from increased favorability of protonation at the distal O position of the key intermediate Co(III)–hydroperoxide species. To interrogate this hypothesis, in this study we have prepared a new Co(III) compound that contains pendent –OMe groups poised to direct protonation toward the proximal O atom of this hydroperoxo intermediate. Mechanistic studies in acetonitrile (MeCN) solution reveal two regimes are possible in the catalytic response, dependent on added acid strength and the presence of the pendent proton donor relay. In the presence of stronger acids, the activity of the complex containing pendent relays becomes O 2 dependent, implying a shift to Co(III)–superoxide protonation as the rate-determining step. Interestingly, the inclusion of the relay results in primarily H 2 O 2 production in MeCN, despite minimal difference between the standard reduction potentials of the three complexes tested. EPR spectroscopic studies indicate the formation of Co(III)–superoxide species in the presence of exogenous base, with greater O 2 reactivity observed in the presence of the pendent –OMe groups.
Iron(III) Nitrate/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Distinguishing between Serial versus Integrated Redox Cooperativity
Aerobic alcohol oxidations catalyzed by transition metal salts and aminoxyls are prominent examples of cooperative catalysis. Cu/aminoxyl catalysts have been studied previously and feature “integrated cooperativity”, in which Cu II and the aminoxyl participate together to mediate alcohol oxidation. Here we investigate a complementary Fe/aminoxyl catalyst system and provide evidence for “serial cooperativity”, involving a redox cascade wherein the alcohol is oxidized by an in situ-generated oxoammonium species, which is directly detected in the catalytic reaction mixture by cyclic step chronoamperometry. The mechanistic difference between the Cu- and Fe-based catalysts arises from the use iron(III) nitrate, which initiates a NO x -based redox cycle for oxidation of aminoxyl/hydroxylamine to oxoammonium. Here, the different mechanisms for the Cu- and Fe-based catalyst systems are manifested in different alcohol oxidation chemoselectivity and functional group compatibility.
Highly Active and Selective Sites for Propane Dehydrogenation in Zeolite Ga-BEA
A highly selective Ga-modified zeolite BEA for propane dehydrogenation has been synthesized by grafting Ga on Zn-BEA followed by removal of Zn in the presence of H 2 . A propene selectivity of 82% at 19% propane conversion illustrates the high selectivity at 813 K. The kinetic model of the catalyzed dehydrogenation including the elementary steps of propane adsorption, first and second C–H bond cleavage, and propene and H 2 desorption demonstrates that the propane dehydrogenation rate is determined by the first C–H bond cleavage at low pC 3 H 8 , while at high pC 3 H 8 , the rate is limited by the desorption of H 2 . The active sites have been identified as dehydrated and tetrahedrally coordinated Ga 3+ in the *BEA lattice. Furthermore, the low selectivity toward aromatics is concluded to be associated with the high Lewis acid strength of lattice Ga 3+ and the low Brønsted acid strength of the hydrated Ga sites.
Gold-Catalyzed Post-Polymerization Modification of Commodity Aromatic Polymers
Not Available
Reversible oxidation and reduction of gold-supported iron oxide islands at room temperature
Monolayer iron oxides grown on metal substrates have widely been used as model systems in heterogeneous catalysis. By means of ambient-pressure scanning tunneling microscopy (AP-STM), we studied the in situ oxidation and reduction of FeO(111) grown on Au(111) by oxygen (O 2 ) and carbon monoxide (CO), respectively. Oxygen dislocation lines present on FeO islands are highly active for O 2 dissociation. X-ray photoelectron spectroscopy measurements distinctly reveal the reversible oxidation and reduction of FeO islands after sequential exposure to O 2 and CO. Here, our AP-STM results show that excess O atoms can be further incorporated on dislocation lines and react with CO, whereas the CO is not strong enough to reduce the FeO supported on Au(111) that is essential to retain the activity of oxygen dislocation lines.
Addressing the sensitivity of signals from solid/liquid ambient pressure XPS (APXPS) measurement
Ambient pressure XPS has demonstrated its great potential in probing the solid/liquid interface, which is a central piece in electrocatalytic, corrosion, and energy storage systems. Additionally, despite the advantage of ambient pressure XPS being a surface sensitive characterization technique, the ability of differentiating the surface adsorbed species (~Å scale) and bulk electrolyte (~10 nm scale) in the spectrum depends on the delicate balance between bulk solution concentration (C), surface coverage (θ), bulk liquid layer thickness (L), and inelastic mean free path (λ) as a function of photon energy. By investigating a model system of gold dissolving in a bromide solution, the connection between theoretical prediction at the atomic resolution and macroscopic observable spectrum is established.
Screening of bimetallic electrocatalysts for water purification with machine learning
Electrocatalysis provides a potential solution to NO 3 - pollution in wastewater by converting it to innocuous N 2 gas. However, materials with excellent catalytic activity are typically limited to expensive precious metals, hindering their commercial viability. Here, in response to this challenge, we have conducted the most extensive computational search to date for electrocatalysts that can facilitate NO 3 - reduction reaction, starting with 59 390 candidate bimetallic alloys from the Materials Project and Automatic-Flow databases. Using a joint machine learning- and computation-based screening strategy, we evaluated our candidates based on corrosion resistance, catalytic activity, N 2 selectivity, cost, and the ability to synthesize. We found that only 20 materials will satisfy all criteria in our screening strategy, all of which contain varying amounts of Cu. Our proposed list of candidates is consistent with previous materials investigated in the literature, with the exception of Cu–Co and Cu–Ag based compounds that merit further investigation.
Preparation of a membrane-sealed cell for studying catalyst nanoparticles in flowing gas with high vacuum x-ray photoelectron spectrometer
Here a sealing-style x-ray photoelectron spectroscopy study of the surface of a 1.0 wt. %Ni/TiO2 nanoparticle catalyst in a flowing mixture of CO and O2 at 1 bar was performed with a graphene membrane-sealed Si3N4 window-based miniature cell. We report the details on how a commercial Si3N4 window is modified before assembling a graphene membrane, how single-layer graphene membranes are transferred from their metal supports to the modified Si3N4 window, how a modified Si3N4 window covered with a double-layer graphene membrane is assembled onto a blank cell cap, how a nanoparticle catalyst is introduced to the cell cap and then the cell cap is installed onto a cell body to form a complete reaction cell, and how a complete cell is interfaced with a high vacuum chamber of an XPS system before an XPS study of 1.0 wt. %Ni/TiO2 catalyst surface in a flowing mixture for 0.2 bar CO and 0.8 bar O2 is performed. How the characterization of a catalyst using this type of graphene membrane-sealed Si3N4 window-based miniature cell is relevant to the finding of the actual surface chemistry of a catalyst during catalysis is discussed.
Prospects for the expansion of standing wave ambient pressure photoemission spectroscopy to reactions at elevated temperatures
Standing wave ambient pressure photoemission spectroscopy (SWAPPS) is a promising method to investigate chemical and potential gradients across solid-vapor and solid-liquid interfaces under close-to-realistic environmental conditions, far away from high vacuum. Until now, these investigations have been performed only near room temperature, but for a wide range of interfacial processes, chief among them being heterogeneous catalysis, measurements at elevated temperatures are required. One concern in these investigations is the temperature stability of the multilayer mirrors, which generate the standing wave field. At elevated temperatures, degradation of the multilayer mirror due to, for example, interdiffusion between the adjacent layers, decreases the modulation of the standing wave field, thus rendering SWAPPS experiments much harder to perform. Here, we show that multilayer mirrors consisting of alternate B4C and W layers are stable at temperatures exceeding 600 °C and are, thus, promising candidates for future studies of surface and subsurface species in heterogeneous catalytic reactions using SWAPPS.
Analysis of nickel sulfoselenide materials by XPS
Metal chalcogenides are of interest as electrocatalysts, battery materials, and more. XPS is a valuable tool for studying changes to these materials before and after catalysis, making reference spectra for the pristine materials valuable. Here, we present XPS spectra for a family of nickel sulfoselenide (NiSSe) materials based on the Ni 3 X 2 crystal structure, Ni 3 S 2-x Se x . XPS surveys and high-resolution spectra of Ni 2p, S 2p, S 2s, Se 3d, Se 3p, and Se 3s were recorded using Al K α radiation.
Fischer-Tropsch Cobalt Catalyst Activation and Handling Through Wax Enclosure Methods
Fischer-Tropsch (F-T) synthesis is considered a gas to liquid process which converts syn-gas, a gaseous mixture of hydrogen and carbon monoxide, into liquids of various hydrocarbon chain length and product distributions. Cobalt based catalysts are used in F-T synthesis and are the focus of this paper. One key concern with handling cobalt based catalysts is that the active form of catalyst is in a reduced state, metallic cobalt, which oxidizes readily in air. In laboratory experiments, the precursor cobalt oxide catalyst is activated in a fixed bed at 350 C then transferred into a continuous stirred tank reactor (CSTR) with inert gas. NASA has developed a process which involves the enclosure of active cobalt catalyst in a wax mold to prevent oxidation during storage and handling. This improved method allows for precise catalyst loading and delivery into a CSTR. Preliminary results indicate similar activity levels in the F-T reaction in comparison to the direct injection method. The work in this paper was supported by the NASA Fundamental Aeronautics Subsonics Fixed Wing Project.
Metal complexes and methods of making the same
Disclosed herein are embodiments of metal complexes and methods of making the same. The disclosed method embodiments provide a one-step approach to making metal complexes, such as complexes comprising lanthanide metals, rare earth metals, transition metals, main group metals, and/or actinide metals that can be used various applications, such as in separations technology, catalysis (e.g., catalysts for pharmaceutical synthesis and/or catalysts for biomass conversion), nuclear chemistry, LED phosphors, scintillator materials, magnetic materials, and nuclear fuels.
Metal–support interactions in metal oxide-supported atomic, cluster, and nanoparticle catalysis
Supported metal catalysts are essential to a plethora of processes in the chemical industry. The overall performance of these catalysts depends strongly on the interaction of adsorbates at the atomic level, which can be manipulated and controlled by the different constituents of the active material (i.e., support and active metal). The description of catalyst activity and the relationship between active constituent and the support, or metal–support interactions (MSI), in heterogeneous (thermo)catalysts is a complex phenomenon with multivariate (dependent and independent) contributions that are difficult to disentangle, both experimentally and theoretically. So-called “strong metal–support interactions” have been reported for several decades and summarized in excellent review articles. However, in recent years, there has been a proliferation of new findings related to atomically dispersed metal sites, metal oxide defects, and, for example, the generation and evolution of MSI under reaction conditions, which has led to the designation of (sub)classifications of MSI deserving to be critically and systematically evaluated. These include dynamic restructuring under alternating redox and reaction conditions, adsorbate-induced MSI, and evidence of strong interactions in oxide-supported metal oxide catalysts. Here, we review recent literature on MSI in oxide-supported metal particles to provide an up-to-date understanding of the underlying physicochemical principles that dominate the observed effects in supported metal atomic, cluster, and nanoparticle catalysts. Critical evaluation of different subclassifications of MSI is provided, along with discussions on the formation mechanisms, theoretical and characterization advances, and tuning strategies to manipulate catalytic reaction performance. We also provide a perspective on the future of the field, and we discuss the analysis of different MSI effects on catalysis quantitatively.
Single Atom Catalysis: An Analogy between Heterogeneous and Homogeneous Catalysts
In recent years, enormous efforts have been invested to improve the atom-efficiency of metal catalysts by decrease the size of metal particles to the limit of isolated atoms in heterogenous catalysis, termed single atom catalysts (SACs). In addition to being atom-efficient, these SACs are increasingly gaining attention due to the unique reactivity and selectivity they have exhibited in industrially relevant reactions, including both oxidation and hydrogenation reactions. Clear parallels can be drawn between heterogeneous SACs and their analogous homogeneous catalysts. In this chapter, we highlight SACs that demonstrate this relationship and report on relevant, recent developments in the field of single atom catalysis.