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At least 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

An Abundant and Diverse New Family of Electron Bifurcating Enzymes With a Non-canonical Catalytic Mechanism

Microorganisms utilize electron bifurcating enzymes in metabolic pathways to carry out thermodynamically unfavorable reactions. Bifurcating FeFe-hydrogenases (HydABC) reversibly oxidize NADH (E′∼−280 mV, under physiological conditions) and reduce protons to H 2 gas (E°′−414 mV) by coupling this endergonic reaction to the exergonic reduction of protons by reduced ferredoxin (Fd) (E′∼−500 mV). We show here that HydABC homologs are surprisingly ubiquitous in the microbial world and are represented by 57 phylogenetically distinct clades but only about half are FeFe-hydrogenases. The others have replaced the hydrogenase domain with another oxidoreductase domain or they contain additional subunits, both of which enable various third reactions to be reversibly coupled to NAD + and Fd reduction. We hypothesize that all of these enzymes carry out electron bifurcation and that their third substrates can include hydrogen peroxide, pyruvate, carbon monoxide, aldehydes, aryl-CoA thioesters, NADP + , cofactor F 420 , formate, and quinones, as well as many yet to be discovered. Some of the enzymes are proposed to be integral membrane-bound proton-translocating complexes. These different functionalities are associated with phylogenetically distinct clades and in many cases with specific microbial phyla. We propose that this new and abundant class of electron bifurcating enzyme be referred to as the Bfu family whose defining feature is a conserved bifurcating BfuBC core. This core contains FMN and six iron sulfur clusters and it interacts directly with ferredoxin (Fd) and NAD(H). Electrons to or from the third substrate are fed into the BfuBC core via BfuA. The other three known families of electron bifurcating enzyme (abbreviated as Nfn, EtfAB, and HdrA) contain a special FAD that bifurcates electrons to high and low potential pathways. The Bfu family are proposed to use a different electron bifurcation mechanism that involves a combination of FMN and three adjacent iron sulfur clusters, including a novel [2Fe-2S] cluster with pentacoordinate and partial non-Cys coordination. The absolute conservation of the redox cofactors of BfuBC in all members of the Bfu enzyme family indicate they have the same non-canonical mechanism to bifurcate electrons. A hypothetical catalytic mechanism is proposed as a basis for future spectroscopic analyses of Bfu family members.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Fe-Exchanged Small-Pore Zeolites as Ammonia Selective Catalytic Reduction (NH 3 -SCR) Catalysts

Cu-exchanged small-pore zeolites have been extensively studied in the past decade as state-of-the-art selective catalytic reduction (SCR) catalysts for diesel engine exhaust NOx abatement for the transportation industry. During this time, Fe-exchanged small-pore zeolites, e.g., Fe/SSZ-13, Fe/SAPO-34, Fe/SSZ-39 and high-silica Fe/LTA, have also been investigated but much less extensively. In comparison to their Cu-exchanged counterparts, such Fe/zeolite catalysts display inferior low-temperature activities, but improved stability and high-temperature SCR selectivities. Such characteristics entitle these catalysts to be considered as key components of highly efficient emission control systems to improve the overall catalyst performance. In this short review, recent studies on Fe-exchanged small-pore zeolite SCR catalysts are summarized, including (1) the synthesis of small-pore Fe/zeolites; (2) nature of the SCR active Fe species in these catalysts as determined by experimental and theoretical approaches, including Fe species transformation during hydrothermal aging; (3) SCR reactions and structure-function correlations; and (4) a few aspects on industrial applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Metal-Catalyzed Thermo-Catalytic Decomposition and Continuous Catalyst Generation

In this study, metal dusting is utilized to initiate a two-stage thermo-catalytic decomposition (TCD) process. Stage 1 starts with metal-catalyzed TCD, and in stage 2 the metal-catalyzed carbon catalyzes additional TCD. TEM is presented of the early- versus late-stage TCD to qualitatively illustrate the second-stage TCD by the metal-catalyzed carbons. Corresponding SEM illustrates differences in growth type and surface density between early versus late reaction times, with backscattered imaging differentiating the first- versus second-stage TCD. TGA supports the microscopic inference of a second carbon phase by the presence of an early (low-temperature) reaction peak, characteristic of low-structure or disordered carbon as the second-stage TCD carbon. Raman analysis confirms that the second-stage carbon deposit is more disordered and unstructured, especially at 1000 °C, supported by the ID/IG and La value changes from 0.068 to 0.936 and 65 nm to 4.7 nm, respectively. To further confirm second-stage TCD occurrence upon pre-catalyzed carbons, two carbon blacks are tested. Exposing a combination of edge and basal or exclusively basal sites for the graphitized form, they afford a direct comparison of TCD carbon nanostructure dependence upon the initial carbon catalyst nanostructure. Pre-oxidation of the stainless-steel wool (SSW) prior to TCD is advantageous, accelerating TCD rates and increasing carbon yield relative to the nascent SSW for an equivalent reaction duration.

Chemistry↗
DOE OSTI2026

Transient Catalytic Reaction Analysis Through Signal Defragmentation

The Temporal Analysis of Products (TAP) pulse response technique provides valuable insights into catalytic function and reaction kinetics. However, complex fragmentation patterns in the TAP mass spectrometry signals can complicate precise quantification, particularly when analyzing transient gas flux data typical of TAP experiments. This work demonstrates a standard defragmentation method that deconvolves transient TAP signals while maintaining the temporal resolution of the experiment. First, the integrals of calibration gas fluxes are used to determine the fingerprint fragmentation pattern and construct a fragmentation matrix. This matrix is then used to defragment experimental flux data at each recorded time point via a non-negative least squares regression. The effectiveness of this method is demonstrated using virtual data and control experiments with a TAP reactor system. The defragmentation is then applied to the more complex propane dehydrogenation reaction on a chromia/alumina catalyst, which can contain up to ten significant gas species in the reactor outlet. Initial propane pulsing reveals an induction period during which propane is fully oxidized to CO2, followed by partial reduction to CO. Afterwards, there is a transition in chemistries towards coking and propylene production. Our example illustrates a practical method for the accurate determination of the time-dependent reactant/product concentrations and rates for a thorough analysis of the propane dehydrogenation kinetics. This approach can be broadly applied to any transient mass spectrometry experiment for a better understanding of catalyst-reaction dynamics.

36 - MATERIALS SCIENCE↗
DOE OSTI2021

Genome-Wide Analysis of Terpene Synthase Gene Family in Mentha longifolia and Catalytic Activity Analysis of a Single Terpene Synthase

Terpenoids are a wide variety of natural products and terpene synthase (TPS) plays a key role in the biosynthesis of terpenoids. Mentha plants are rich in essential oils, whose main components are terpenoids, and their biosynthetic pathways have been basically elucidated. However, there is a lack of systematic identification and study of TPS in Mentha plants. In this work, we genome-widely identified and analyzed the TPS gene family in Mentha longifolia, a model plant for functional genomic research in the genus Mentha. A total of 63 TPS genes were identified in the M. longifolia genome sequence assembly, which could be divided into six subfamilies. The TPS-b subfamily had the largest number of genes, which might be related to the abundant monoterpenoids in Mentha plants. The TPS-e subfamily had 18 members and showed a significant species-specific expansion compared with other sequenced Lamiaceae plant species. The 63 TPS genes could be mapped to nine scaffolds of the M. longifolia genome sequence assembly and the distribution of these genes is uneven. Tandem duplicates and fragment duplicates contributed greatly to the increase in the number of TPS genes in M. longifolia. The conserved motifs (RR(X)8W, NSE/DTE, RXR, and DDXXD) were analyzed in M. longifolia TPSs, and significant differentiation was found between different subfamilies. Adaptive evolution analysis showed that M. longifolia TPSs were subjected to purifying selection after the species-specific expansion, and some amino acid residues under positive selection were identified. Furthermore, we also cloned and analyzed the catalytic activity of a single terpene synthase, MlongTPS29, which belongs to the TPS-b subfamily. MlongTPS29 could encode a limonene synthase and catalyze the biosynthesis of limonene, an important precursor of essential oils from the genus Mentha. This study provides useful information for the biosynthesis of terpenoids in the genus Mentha.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

On the Nature of Extra-Framework Aluminum Species and Improved Catalytic Properties in Steamed Zeolites

Steamed zeolites exhibit improved catalytic properties for hydrocarbon activation (alkane cracking and dehydrogenation). The nature of this practically important phenomenon has remained a mystery for the last six decades and was suggested to be related to the increased strength of zeolitic Bronsted acid sites after dealumination. We now utilize state-of-the-art infrared spectroscopy measurements and prove that during steaming, aluminum oxide clusters evolve (due to hydrolysis of Al out of framework positions with the following clustering) in the zeolitic micropores with properties very similar to (nano) facets of hydroxylated transition alumina surfaces. The Bronsted acidity of the zeolite does not increase and the total number of Bronsted acid sites decreases during steaming. O 5 Al(VI)-OH surface sites of alumina clusters dehydroxylate at elevated temperatures to form penta-coordinate Al 1 O 5 sites that are capable of initiating alkane cracking by breaking the first C-H bond very effectively with much lower barriers (at lower temperatures) than for protolytic C-H bond activation, with the following reaction steps catalyzed by nearby zeolitic Bronsted acid sites. This explains the underlying mechanism behind the improved alkane cracking and alkane dehydrogenation activity of steamed zeolites: heterolytic C-H bond breaking occurs on Al-O sites of aluminum oxide clusters confined in zeolitic pores. Our findings explain the origin of enhanced activity of steamed zeolites at the molecular level and provide the missing understanding of the nature of extra-framework Al species formed in steamed/dealuminated zeolites.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2026

Exploration of the Electronic and Catalytic Properties of [Co 5 MS 8 (PEt 3 ) 5 ] 1+ Nanoclusters: A Computational Study

Recent studies have demonstrated the relative stability of undercoordinated hexanuclear cobalt sulfide nanoclusters (NCs) with different charge states. Considering that these small metal NCs have atomically precise structures and high reactivity due to the open shell of the transition metals, and provide selectivity toward ligand loss, they are a vital model for catalysis. In this paper, the electronic structures of these NCs are investigated. These NCs are then used as the reference state to analyze the catalytic properties with respect to hydrogen evolution reaction (HER) and CO 2 reduction (CO 2 R). Further, to understand the effect of heteroatom incorporation, the geometry and reactivity of ten different metal dopants are analyzed. This work shows that the type of metal incorporation greatly affects the electronic structure and formation energies for ligand binding and catalysis. Particularly, the d-orbital occupancy in the cobalt atoms remains largely unchanged, while the heteroatom greatly influences the reactivity of the undercoordinated NCs. Most notably, this work highlights that transition metals in [Co 5 MS 8 (PEt 3 ) 5 ] 1+ NCs would competitively prefer electrochemical adsorption of H over COOH, while the main group metals prefer COOH adsorption.

catalysis↗
DOE OSTI2025

Characterization of Kariya ( Hildegardia barteri (Mast.) Kosterm) Seed Oil Fatty Acid Methyl Ester Prepared from Basic Catalytic Transesterification

The rising global energy demand, alongside concerns regarding environmental deterioration due to the use of fossil fuels, has spurred extensive investigation into renewable energy alternatives. Biomass-derived biodiesel, especially from lesser-known oil sources, emerges as a promising option. This research focuses on analyzing the fatty acid methyl esters (FAMEs) derived from Kariya (Hildegardia barteri (Mast.) Kosterm) seed oil through basic catalytic transesterification using gas chromatography–flame ionization detector (GC–FID) analysis, assessing its potential as a biodiesel feedstock. Oil extraction from Kariya seeds was carried out using three solvents (n-hexane, ethanol, and a 1:1 blend of hexane and ethanol), followed by transesterification with methanol. Gas chromatography–mass spectrometry (GC–MS) and GC–FID analyses were utilized to identify and quantify FAMEs in the resulting biodiesel. The results revealed various FAMEs, including methyl myristate, methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, and methyl linolenate. Significant differences in FAME composition were observed among the samples, with hexane–ethanol Kariya oil biodiesel (HE-KOB) showing the highest FAME content (76.1%). This combination of solvents exhibited synergistic effects on the composition of HE-KOB, suggesting potential optimization strategies for biodiesel production. Fourier transform infrared spectroscopy (FTIR) provided additional insights into the molecular composition of the biodiesel samples, confirming their biodiesel nature through the identified functional groups such as methyl, methylene, hydrocarbon, ester, aldehyde, and alkene. Thermogravimetric analysis (TGA) for thermal decomposition also gave an insight into FAME composition and its contribution to the degree of conversion of biodiesel to energy. These findings highlight the feasibility of utilizing Kariya seed oil as a biodiesel feedstock, emphasizing the importance of solvent selection and transesterification conditions in optimizing FAME yield and composition. This research contributes to the exploration of underutilized oil sources for sustainable biodiesel production, aligning with the global shift towards cleaner and renewable energy sources.

09 BIOMASS FUELS↗
DOE OSTI2021

Effects of Hybridization on Selective Catalytic Reduction (SCR) Thermal Management of a Medium Heavy-Duty Hybrid Work Truck

The increased market penetration of hybrid electric powertrains in medium heavy-duty (MHD) applications has provided a novel platform for vehicle research. One example of such a platform is the MHD parallel hybrid truck developed by Odyne Systems, LLC. In collaboration with Odyne Systems, LLC and the Department of Energy (DOE), Oak Ridge National Laboratory (ORNL) developed a validated vehicle plant model for this truck and tested the Odyne powertrain in a hardware-in-the-loop (HIL) environment. While testing in the HIL environment, the effects of reduced engine load, and thus catalyst heating, on the selective catalytic reduction (SCR) catalyst produced diminished hybrid improvement as the level of energy storage usage increased. This article will discuss these results and the potentially unforeseen interactions with modern aftertreatment systems when hybridizing conventional powertrains.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2021

Performance Comparison of LPG and Gasoline in an Engine Configured for EGR-Loop Catalytic Reforming

In prior work, the EGR loop catalytic reforming strategy developed by ORNL has been shown to provide a relative brake engine efficiency increase of more than 6% by minimizing the thermodynamic expense of the reforming processes, and in some cases achieving thermochemical recuperation (TCR), a form of waste heat recovery where waste heat is converted to usable chemical energy. In doing so, the EGR dilution limit was extended beyond 35% under stoichiometric conditions. In this investigation, a Microlith®-based metal-supported reforming catalyst (developed by Precision Combustion, Inc. (PCI)) was used to reform the parent fuel in a thermodynamically efficient manner into products rich in H2 and CO. We were able to expand the speed and load ranges relative to previous investigations: from 1,500 to 2,500 rpm, and from 2 to 14 bar break mean effective pressure (BMEP). Experiments were conducted to determine the effects of the H/C ratio of the fuel on H2 production and on the engine efficiency in order to compare E10 gasoline (H/C = 1.95) and liquified petroleum gas (LPG), comprised primarily of propane (H/C = 2.67). Additionally, the compression ratio of the engine was increased to ascertain whether further efficiency improvements could be realized based on a reduced knock propensity of the dilute EGR mixture with the reformed fuel. Both the gasoline and propane reforming strategies provided efficiency gains up to 1.85 percentage points and further efficiency improvements with the increased compression ratio were realized. The fuel specific effects of gasoline vs. LPG, the effect of engine operating condition on reforming, and knock limits of the reformed mixture are discussed in detail.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2021

Co-Processing Catalytic Fast Pyrolysis Oil in an FCC Reactor

Studies of co-processing catalytic fast pyrolysis (CFP) oil with vacuum gas oil (VGO) are conducted in a Davison Circulating Riser (DCR). The CFP oil (CFPO) for this study was produced by upgrading fast-pyrolysis vapors from pine in an ex-situ fixed-bed reactor. CFPOs were co-processed at up to 5 vol% with VGO at 521°C and 2.57 bar. The yields of oil, aqueous phase, tail gas, and coke were measured. The amount of coke was determined from the carbon containing components in the regenerator flue gas. A compositional analysis was conducted with gas chromatography and elemental analyzers. The organic liquids were distilled into gasoline, jet-fuel, diesel, and resid fractions. A biocarbon analysis was conducted on the organic phase and its individual boiling-point fractions. The results show a small decrease in liquid yield and a generally increased gas yield when co-processing CFPO with VGO. For experiments with E-Cat as catalyst, approximately 70% of biocarbon is incorporated into liquid fuels relative to fossil carbon, while more of the biocarbon is contained in tail gas (as carbon dioxide or olefins) and/or coke. The measurements indicate that cracked CFPO components are predominantly included in the jet-fuel and diesel fractions. A techno-economic analysis (TEA) estimated the minimum fuel selling price (MSFP) for fuel-range products derived from FCC co-processing of CFPO at $3 to $4 per gasoline-gallon equivalent (GGE) at a yield of 51 GGE per ton of biomass.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2020

Separation of High Purity Oxygenated Aromatics from Catalytic Fast Pyrolysis Organic Streams

Thermochemical conversion of lignocellulosic biomass offers an attractive route to produce fuels and chemicals. Specifically, catalytic fast pyrolysis (CFP) oils have been shown to contain a high concentration of oxygenated aromatics, which can be isolated as value-added co-products. Purification of oxygenated aromatics can be a viable pathway to more economically competitive biorefineries, yet the isolation of highly pure coproduct streams remains technically challenging due to the high chemical heterogeneity of thermochemical process steams. Here, we demonstrate an industrially scalable process for isolating phenol, a widely used precursor to plastics, from CFP oil. Importantly, we leverage standard industrial processes, such as distillation, liquid-liquid extraction, and crystallization, to achieve phenol with 97% purity. In addition, the primary distillation of the CFP oil yielded several other fractions that contain chemicals with the potential to be isolated (e.g. cyclic ketones, cresols, and guaiacols). This work provides a technically feasible path to high purity oxygenated aromatics that has the potential to offset fuel production costs in a biorefinery.

09 BIOMASS FUELS↗
DOE OSTI2020

Zeolitic catalytic conversion of alcohols to hydrocarbon fractions with reduced gaseous hydrocarbon content

A method for converting an alcohol to a hydrocarbon fraction reduced in gaseous hydrocarbon content, the method comprising: (i) contacting said alcohol with a metal-loaded zeolite catalyst under conditions suitable for converting said alcohol to a first hydrocarbon fraction containing liquid hydrocarbons having at least five carbon atoms along with gaseous hydrocarbons having less than five carbon atoms, wherein said metal-loaded zeolite catalyst is catalytically active for converting said alcohol to said first hydrocarbon fraction; and (ii) selectively removing said gaseous hydrocarbons from the first hydrocarbon fraction and contacting said gaseous hydrocarbons with a metal-loaded zeolite catalyst under conditions suitable for converting said gaseous hydrocarbons into liquid hydrocarbons having at least five carbon atoms to produce a second hydrocarbon fraction reduced in gaseous hydrocarbon content, wherein the metal-loaded zeolite catalyst in steps (i) and (ii) are the same or different.

09 BIOMASS FUELS↗
DOE OSTI2020

Fuel Property-Informed Process Design for the Direct Catalytic Conversion of Cellulosics

The direct catalytic conversion of cellulosics (DC3) with supercritical methanol presents a promising pathway to completely solubilize woody biomass and produce >60% mass yield of C2-C6 oxygenates for light duty vehicle applications. Although the oxygenate composition can be tuned by modifying catalyst and process conditions, limited efforts to date have examined DC3 fuel properties for light duty fuel applications to iteratively inform conversion process design. In this work, we designed and evaluated multi-component surrogate bioblendstocks that represent major DC3 light oxygenates and refined catalyst formulations and distillation parameters to improve the resulting light duty fuel quality. Surrogate design for this novel fuel production pathway was based on a preliminary product slate that was systematically adjusted to determine impacts on fuel properties of interest including heating value, oxidative stability, and heat of vaporization, among others. The resulting predictions and measurements of these surrogates were then used to inform improvement of conversion process, and specifically, reformulation of the catalyst which resulted in production of a higher energy density fuel product primarily comprised of saturated alcohols. Fuel testing outcomes also informed downstream oxygenate separations requirements. This resulted in the production of a promising DC3 light-duty fuel blendstock with >15% greater energy density relative to ethanol, while maintaining high octane number and octane sensitivity.

BIOMASS FUELS↗
DOE OSTI2021

Metal-organic frameworks for the adsorption and catalytic transformations of carbon dioxide

Novel crystalline porous materials known as metal-organic frameworks (MOFs) and methods for their synthesis are provided herein. The MOFs include a M6(μ3-OH)8(OH)8(μ2,η2-(O2C)2cyclam)8 cluster, and a metal atom coordinated to the one or more cyclam of the cluster, wherein M is Zr or Hf, and the metal atom is any one of Cu, Ni, Cr, Ru, Co, and Gd. The MOFs can be used as an adsorbent, alone or in a medium with other components, of CO2. The MOFs can also be used as a catalyst for the transformation of CO2 and epoxides to cyclic carbonates. The MOFs can also be used in the electrochemical catalytic reduction of CO2. The MOFs can also be used for photocatalytic CO2 reduction for the production of carbon-based fossil fuels. The MOFs can also be used for light-induced nitric oxide (NO) release. The MOFs can also be used as magnetic resonance imaging (MRI) agents.

Morris, Amanda Jean↗
DOE OSTI2022

Catalytic synthesis of super linear alkenyl arenes using rhodium catalysts

Catalytic methods for synthesis of super linear alkenyl arenes and alkyl arenes are provided. The methods are capable of synthesizing super linear alkyl and alkenyl arenes from simple arene and olefin starting materials and with high selectivity for linear coupling. Methods are also provided for making a 2,6-dimethylnapthalene (DMN) or 2,6-methylethylnapthalene (MEN).

Schinski, William↗