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Results for “methane oxidation”

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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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Large freshwater phages with the potential to augment aerobic methane oxidation

There is growing evidence that phages with unusually large genomes are common across various microbiomes, but little is known about their genetic inventories or potential ecosystem impacts. In the present study, we reconstructed large phage genomes from freshwater lakes known to contain bacteria that oxidize methane. Of manually curated genomes, 22 (18 are complete), ranging from 159 kilobase (kb) to 527 kb in length, were found to encode the pmoC gene, an enzymatically critical subunit of the particulate methane monooxygenase, the predominant methane oxidation catalyst in nature. The phage-associated PmoC sequences show high similarity to (>90%), and affiliate phylogenetically with, those of coexisting bacterial methanotrophs, including members of Methyloparacoccus, Methylocystis and Methylobacter spp. In addition, pmoC-phage abundance patterns correlate with those of the coexisting bacterial methanotrophs, supporting host–phage relationships. Future work is needed to determine whether phage-associated PmoC has similar functions to additional copies of PmoC encoded in bacterial genomes, thus contributing to growth on methane. Transcriptomics data from Lake Rotsee (Switzerland) showed that some phage-associated pmoC genes were highly expressed in situ and, of interest, that the most rapidly growing methanotroph was infected by three pmoC-phages. Thus, augmentation of bacterial methane oxidation by pmoC-phages during infection could modulate the efflux of this potent greenhouse gas into the environment.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Selective Formation of Acetic Acid and Methanol by Direct Methane Oxidation Using Rhodium Single-Atom Catalysts

Atomically dispersed catalysts such as single-atom catalysts have been shown to be effective in selectively oxidizing methane, promising a direct synthetic route to value-added oxygenates such as acetic acid or methanol. However, an important challenge of this approach has been that the loading of active sites by single-atom catalysts is low, leading to a low overall yield of the products. We report an approach that can address this issue. It utilizes a metal–organic framework built with porphyrin as the linker, which provides high concentrations of binding sites to support atomically dispersed rhodium. It is shown that up to 5 wt% rhodium loading can be achieved with excellent dispersity. When used for acetic acid synthesis by methane oxidation, a new benchmark performance of 23.62 mmol·gcat –1 ·h –1 was measured. Furthermore, the catalyst exhibits a unique sensitivity to light, producing acetic acid (under illumination, up to 66.4% selectivity) or methanol (in the dark, up to 65.0% selectivity) under otherwise identical reaction conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Selective Methane Oxidation by Heterogenized Iridium Catalysts

Oxidative methane (CH 4 ) carbonylation promises a direct route to the synthesis of value-added oxygenates such as acetic acid (CH 3 COOH). Here, in this paper, we report a strategy to realize oxidative CH 4 carbonylation through immobilized Ir complexes on an oxide support. Our immobilization approach not only enables direct CH 4 activation but also allows for easy separation and reutilization of the catalyst. Furthermore, we show that a key step, methyl migration, that forms a C–C bond, is sensitive to the electrophilicity of carbonyl, which can be tuned by a gentle reduction to the Ir centers. While the as-prepared catalyst that mainly featured Ir(IV) preferred CH 3 COOH production, a reduced catalyst featuring predominantly Ir(III) led to a significant increase of CH 3 OH production at the expense of the reduced yield of CH 3 COOH.

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

Carbonate-hosted microbial communities are prolific and pervasive methane oxidizers at geologically diverse marine methane seep sites

At marine methane seeps, vast quantities of methane move through the shallow subseafloor, where it is largely consumed by microbial communities. This process plays an important role in global methane dynamics, but we have yet to identify all of the methane sinks in the deep sea. Here, we conducted a continental-scale survey of seven geologically diverse seafloor seeps and found that carbonate rocks from all sites host methane-oxidizing microbial communities with substantial methanotrophic potential. In laboratory-based mesocosm incubations, chimney-like carbonates from the newly described Point Dume seep off the coast of Southern California exhibited the highest rates of anaerobic methane oxidation measured to date. After a thorough analysis of physicochemical, electrical, and biological factors, we attribute this substantial metabolic activity largely to higher cell density, mineral composition, kinetic parameters including an elevated V max , and the presence of specific microbial lineages. Our data also suggest that other features, such as electrical conductance, rock particle size, and microbial community alpha diversity, may influence a sample’s methanotrophic potential, but these factors did not demonstrate clear patterns with respect to methane oxidation rates. Based on the apparent pervasiveness within seep carbonates of microbial communities capable of performing anaerobic oxidation of methane, as well as the frequent occurrence of carbonates at seeps, we suggest that rock-hosted methanotrophy may be an important contributor to marine methane consumption.

58 GEOSCIENCES↗
DOE OSTI2021

Activity of Cu-Al-oxo extra-framework clusters for selective methane oxidation on Cu exchanged zeolites

Cu-zeolites are able to directly convert methane to methanol via a 3-step process using O2 as oxidant. Among the different zeolite topologies, Cu-exchanged mordenite (MOR) shows the highest methanol yields, attributed to a preferential formation of active Cu-oxo species in its 8-MR pores. The presence of extra-framework or partially detached Al species entrained in the micropores of MOR leads to the formation of nearly homotopic redox active Cu-Al-oxo nanoclusters with the ability to activate CH4. Studies of the activity of these sites together with characterization by 27Al NMR and IR spectroscopy leads to the conclusion that the active species are located in the 8-MR side pockets of MOR and it consists of two Cu ions and one Al linked by O. This Cu-Al oxo cluster shows an activity per Cu in methane oxidation significantly higher than of any previ-ously reported active Cu-oxo species. In order to determine unambiguously the structure of the active Cu-Al-oxo cluster, we combine experimental XANES of Cu K- and L- edges, Cu K-edge HERFD-XANES and Cu K-edge EXAFS with TDDFT and AIMD-assisted simulations. Our results provide evidence of a [Cu2AlO3]2+ cluster exchanged on MOR Al pairs that is able to oxidize up to two methane molecules per cluster at ambient pressure.

Methane oxidation, Cu L3-edge XANES, HERFD, TDDFT,↗
DOE OSTI2024

Redox dynamics and surface structures of an active palladium catalyst during methane oxidation

Catalysts based on palladium are among the most effective in the complete oxidation of methane. Despite extensive studies and notable advances, the nature of their catalytically active species and conceivable structural dynamics remains only partially understood. Here, we combine operando transmission electron microscopy (TEM) with near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory (DFT) calculations to investigate the active state and catalytic function of Pd nanoparticles (NPs) under methane oxidation conditions. We show that the particle size, phase composition and dynamics respond appreciably to changes in the gas-phase chemical potential. In combination with mass spectrometry (MS) conducted simultaneously with in situ observations, we uncover that the catalytically active state exhibits phase coexistence and oscillatory phase transitions between Pd and PdO. Aided by DFT calculations, we provide a rationale for the observed redox dynamics and demonstrate that the emergence of catalytic activity is related to the dynamic interplay between coexisting phases, with the resulting strained PdO having more favorable energetics for methane oxidation.

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

Anaerobic methane oxidation coupled to manganese reduction by members of the Methanoperedenaceae

Abstract Anaerobic oxidation of methane (AOM) is a major biological process that reduces global methane emission to the atmosphere. Anaerobic methanotrophic archaea (ANME) mediate this process through the coupling of methane oxidation to different electron acceptors, or in concert with a syntrophic bacterial partner. Recently, ANME belonging to the archaeal family Methanoperedenaceae (formerly known as ANME-2d) were shown to be capable of AOM coupled to nitrate and iron reduction. Here, a freshwater sediment bioreactor fed with methane and Mn(IV) oxides (birnessite) resulted in a microbial community dominated by two novel members of the Methanoperedenaceae, with biochemical profiling of the system demonstrating Mn(IV)-dependent AOM. Genomic and transcriptomic analyses revealed the expression of key genes involved in methane oxidation and several shared multiheme c-type cytochromes (MHCs) that were differentially expressed, indicating the likely use of different extracellular electron transfer pathways. We propose the names “Candidatus Methanoperedens manganicus” and “Candidatus Methanoperedens manganireducens” for the two newly described Methanoperedenaceae species. This study demonstrates the ability of members of the Methanoperedenaceae to couple AOM to the reduction of Mn(IV) oxides, which suggests their potential role in linking methane and manganese cycling in the environment.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Catalyst Deactivation Modes of PdO/γ-Al 2 O 3 Catalysts for Lean Methane Oxidation

PdO/γ-Al 2 O 3 catalysts are one of the most active catalytic components for the complete oxidation of methane. Under reaction conditions, especially in a wet feed, the catalysts suffer severe performance degradation. This study establishes a series of testing protocols to systematically investigate the causes of catalyst deactivation under methane oxidation reaction conditions. Four distinct catalyst deactivation modes are identified. Two of the deactivation modes are directly related to H 2 O, either from the feed gas or as a part of the reaction products, with one (Mode 2) being attributed to the formation of surface hydroxyl groups and the other (Mode 3) to the competitive adsorption of H 2 O on the catalysts. The impact of the two deactivation modes is acute and severe but reversible. In contrast, the other two deactivation modes are gradual and persistent but irreversible. Both modes are induced by CH 4 oxidation reaction, with the impact of a wet feed (Mode 4) being substantially more severe than that of a dry feed (Mode 1). The major cause of the irreversible catalyst deactivation is attributed to surface reconstruction of PdO nanoparticles, which behaves as a passivation layer lowering the number of coordinately unsaturated Pd sites for CH 4 activation. Although the passivation layer is relatively stable against thermal or hydrothermal treatment, it is not completely inert. Formation and partial regeneration of the passivation layer is a highly dynamic process and heavily depends on the reaction temperature: a lower reaction temperature (≤ 450 ℃) can lead to quicker catalyst deactivation; but a higher reaction temperature (between 500 – 550 ℃) can result in a greater extent of catalyst deactivation.

PdO/γ-Al2O3↗
DOE OSTI2024

In situ aerobic methane oxidation rates in a stratified lake

Abstract Microbial aerobic methane oxidation is an important sink for aquatic methane worldwide. Despite its importance to global methane fluxes, few aerobic methane oxidation rates have been obtained in freshwater or marine environments without imposing changes to the microbial community through use of ex situ methods. A novel in situ incubation method for continuous time‐series measurements was used in Jordan Lake, North Carolina, during 2020–2021, to determine reaction kinetics for aerobic methane oxidation rates across a wide range of naturally varying methane (55–1833 nM) and dissolved oxygen (DO; 28–366 μM) concentrations and temperatures (17–30°C). Methane oxidation began immediately at the start of each of 21 incubations and methane oxidation rates were 1 st order with respect to methane. The data density allowed for accurate calculation of 1 st ‐order rate constants,k, that ranged from 0.018 to 0.462 h −1 (R 2 > 0.967). Addition of ammonium (20–45 μM) to natural concentrations ranging from 0.057 to 2.4 μM did not change aerobic methane oxidation rate kinetics, suggesting that the natural population of aerobic methane oxidizers in this eutrophic lake was not nitrogen limited. Values ofkinversely correlated most strongly with initial DO concentrations (R 2 = 0.82) rather than temperature. Values forkincreased with Julian day throughout our sampling period, suggesting seasonal influences on methane oxidation via responses to geochemical changes or shifts in microbial community abundance and composition. These experiments demonstrate a high variability in the enzymatic capacity for 1 st ‐order methane oxidation rates in this eutrophic lake that is tightly and inversely coupled to oxygen concentrations. Measurements of in situ aerobic methane oxidation rate constants allow for the direct quantification and modeling of the microbial community's capacity for methane oxidation over a wide range of natural methane concentrations.

Marine & Freshwater Biology↗
DOE OSTI2024

Hydrothermally stable methane oxidation catalyst

A method of manufacturing a methane oxidation catalyst and methane oxidation catalysts formed by the method are provided. The method includes providing a palladium (Pd)-based catalyst including Pd dispersed onto a support. A magnesium (Mg) precursor is introduced to the Pd-based catalyst by one of ion exchange or incipient wetness impregnation. After introducing the magnesium precursor to the Pd-based catalyst, the catalyst is dried and subjected to a final heat treatment that includes hydrothermal calcination. A method of methane oxidation in a lean exhaust environment via the methane oxidation catalyst is also provided.

DeBusk, Melanie M.↗
DOE OSTI2023

Microbially induced precipitation of silica by anaerobic methane-oxidizing consortia and implications for microbial fossil preservation

Authigenic carbonate minerals can preserve biosignatures of microbial anaerobic oxidation of methane (AOM) in the rock record. It is not currently known whether the microorganisms that mediate sulfate-coupled AOM—often occurring as multicelled consortia of anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB)—are preserved as microfossils. Electron microscopy of ANME-SRB consortia in methane seep sediments has shown that these microorganisms can be associated with silicate minerals such as clays [Chen et al., Sci. Rep. 4, 1–9 (2014)], but the biogenicity of these phases, their geochemical composition, and their potential preservation in the rock record is poorly constrained. Long-term laboratory AOM enrichment cultures in sediment-free artificial seawater [Yu et al., Appl. Environ. Microbiol. 88, e02109-21 (2022)] resulted in precipitation of amorphous silicate particles (~200 nm) within clusters of exopolymer-rich AOM consortia from media undersaturated with respect to silica, suggestive of a microbially mediated process. The use of techniques like correlative fluorescence in situ hybridization (FISH), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), and nanoscale secondary ion mass spectrometry (nanoSIMS) on AOM consortia from methane seep authigenic carbonates and sediments further revealed that they are enveloped in a silica-rich phase similar to the mineral phase on ANME-SRB consortia in enrichment cultures. Like in cyanobacteria [Moore et al., Geology 48, 862–866 (2020)], the Si-rich phases on ANME-SRB consortia identified here may enhance their preservation as microfossils. Finally, the morphology of these silica-rich precipitates, consistent with amorphous-type clay-like spheroids formed within organic assemblages, provides an additional mineralogical signature that may assist in the search for structural remnants of microbial consortia in rocks which formed in methane-rich environments from Earth and other planetary bodies.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Decoupling plasma, catalyst, and gaseous mechanisms for non-oxidative methane conversion

Direct non-oxidative methane (CH 4 ) conversion to value-added hydrogen (H 2 ) and C 2 products remains hindered by fundamental catalytic scaling constraints and rapid surface deactivation at elevated temperatures. Plasma-enabled catalysis offers a promising route to overcome the thermodynamic and kinetic barriers of direct non-oxidative methane upgrading at mild conditions, yet control over C–C product selectivity and catalyst stability remains elusive. Here, we establish a unified mechanistic framework including Langmuir–Hinshelwood (L–H) and Langmuir–Rideal (L–R) mechanisms that disentangles the roles of plasma excitation (including vibrationally activated species and radicals), surface temperature (T sur ), and catalyst binding energy in steering CH 4 conversion to H 2 and C 2 hydrocarbons. Through a combination of density functional theory (DFT) informed microkinetic modeling, in situ and ex situ surface characterization, and product quantification under dielectric barrier discharge conditions, we show that vibrationally excited CH 4 lowers activation barriers selectively for dissociative chemisorption, enabling surface activation across a wide range of transition metal catalysts at low thermal energy input. We find that once CH 4 is dissociatively chemisorbed, the branching between C 2 H 2 , C 2 H 4 , and C 2 H 6 is governed by surface properties (carbon binding energy, T sur , etc), regardless of plasma excitation. The DFT informed microkinetic model decouples the effects of molecular activation from surface properties and indentifies operating windows that maximize target yields while suppressing carbon accumulation and subsequent catalytic inactivation. Experiments on polycrystalline Cu/Al 2 O 3 , Ni/Al 2 O 3 , and Pt/Al 2 O 3 validate these predictions, revealing catalyst-dependent branching toward ethane or ethylene and distinct deactivation profiles. We unify these trends into a generalized three-dimensional plasma-thermal-catalytic design space, from which reduced descriptors such as T vib /T sur in the limit of vibrationally excited L–H pathways emerge as predictive metrics. These results enable rational tuning of methane conversion pathways and unlock selective C 2 formation using earth-abundant metals under mild plasma conditions.

catalyst inactivation↗
DOE OSTI2024

Mechanistic and Kinetic Analysis of Complete Methane Oxidation on a Practical PtPd/Al 2 O 3 Catalyst

A PtPd/Al 2 O 3 catalyst developed for the complete oxidation of methane from the ventilation air of underground coal mines is compared against a model PdO/Al 2 O 3 catalyst. Although the PtPd/Al 2 O 3 catalyst is substantially more active and stable than the model catalyst, the nature of active sites between the two catalysts is deemed to be fundamentally the same based on their response to different feed gas compositions and the evolution of surface CO adsorption complexes during time-resolved CO adsorption DRIFTS experiment. For both catalysts, coordinatively unsaturated Pd sites are considered the active centers for methane activation and the subsequent oxidation reaction. H 2 O competes with CH 4 for the same active sites, resulting in severe inhibition. Additionally, the CH 4 oxidation reaction also causes self-inhibition. Taking both inhibition effects into consideration, a relatively simple kinetic model is developed. The model provides a good fit of the 72 sets of kinetic data collected on the PtPd/Al 2 O 3 catalyst under practically relevant reaction conditions with CH 4 concentration in the range of 0.05–0.4%, H 2 O concentration of 1.0–5.0%, and reaction temperatures of 450–700 °C. Kinetic parameters based on the model suggest that the CH 4 activation energy on the PtPd/Al 2 O 3 catalyst is 96.7 kJ/mol, and the H 2 O adsorption energy is –31.0 kJ/mol. Both values are consistent with the parameters reported in the literature. The model can be used to develop catalyst sizing guidelines and be incorporated into the control algorithm of the catalytic system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Understanding the Impact of Hydrogen Activation by SrCe 0.8 Zr 0.2 O 3-δ Perovskite Membrane Material on Direct Non-Oxidative Methane Conversion

Direct non-oxidative methane conversion (DNMC) converts methane (CH 4 ) in one step to olefin and aromatic hydrocarbons and hydrogen (H 2 ) co-product. Membrane reactors comprising methane activation catalysts and H 2 -permeable membranes can enhance methane conversion by in situ H 2 removal via Le Chatelier's principle. Rigorous description of H 2 kinetic effects on both membrane and catalyst materials in the membrane reactor, however, has been rarely studied. In this work, we report the impact of hydrogen activation by hydrogen-permeable SrCe 0.8 Zr 0.2 O 3-δ (SCZO) perovskite oxide material on DNMC over an iron/silica catalyst. The SCZO oxide has mixed ionic and electronic conductivity and is capable of H 2 activation into protons and electrons for H 2 permeation. In the fixed-bed reactor packed with a mixture of SCZO oxide and iron/silica catalyst, stable and high methane conversion and low coke selectivity in DNMC was achieved by co-feeding of H 2 in methane stream. The characterizations show that SCZO activates H 2 to favor “soft coke” formation on the catalyst. The SCZO could absorb H 2 in situ to lower its local concentration to mitigate the reverse reaction of DNMC in the tested conditions. The co-existence of H 2 co-feed, SCZO oxide, and DNMC catalyst in the present study mimics the conditions of DNMC in the H 2 -permeable SCZO membrane reactor. The findings in this work offer the mechanistic understanding of and guidance for the design of H 2 -permeable membrane reactors for DNMC and other alkane dehydrogenation reactions.

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

Climate-induced shifts in sulfate dynamics regulate anaerobic methane oxidation in a coastal wetland

Anaerobic methane oxidation (AMO) is a key microbial pathway that mitigates methane emissions in coastal wetlands, but the response of AMO to changing global climate remains poorly understood. Here, we assessed the response of AMO to climate change in a brackish coastal wetland using a 5-year field manipulation of warming and elevated carbon dioxide ( e CO 2 ). Sulfate (SO 4 2− )–dependent AMO (S-DAMO) was the predominant AMO process at our study site due to tidal inputs of SO 4 2− . However, SO 4 2− dynamics responded differently to the treatments; warming reduced SO 4 2− concentration by enhancing SO 4 2− reduction, while eCO 2 increased SO 4 2− concentration by enhancing SO 4 2− regeneration. S-DAMO rates mirrored these trends, with warming decreasing S-DAMO rates and e CO 2 stimulating them. These findings underscore the potential of climate change to alter soil AMO activities through changing SO 4 2− dynamics, highlighting the need to incorporate these processes in predictive models for more accurate representations of coastal wetland methane dynamics.

54 ENVIRONMENTAL SCIENCES↗