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NASA NTRS2020

Climate and air quality impacts due to mitigation of non-methane near-term climate forcers

It is important to understand how future environmental policies will impact both climate change and air pollution. Although targeting near-term climate forcers (NTCFs), defined here as aerosols, tropospheric ozone, and precursor gases, should improve air quality, NTCF reductions will also impact climate. Prior assessments of the impact of NTCF mitigation on air quality and climate have been limited. This is related to the idealized nature of some prior studies, simplified treatment of aerosols and chemically reactive gases, as well as a lack of a sufficiently large number of models to quantify model diversity and robust responses. Here, we quantify the 2015–2055 climate and air quality effects of non-methane NTCFs using nine state-of-the-art chemistry–climate model simulations conducted for the Aerosol and Chemistry Model Intercomparison Project (AerChemMIP). Simulations are driven by two future scenarios featuring similar increases in greenhouse gases (GHGs) but with “weak” (SSP3-7.0) versus “strong” (SSP3-7.0-lowNTCF) levels of air quality control measures. As SSP3-7.0 lacks climate policy and has the highest levels of NTCFs, our results (e.g., surface warming) represent an upper bound. Unsurprisingly, we find significant improvements in air quality under NTCF mitigation (strong versus weak air quality controls). Surface fine particulate matter (PM2.5) and ozone (O3) decrease by −2.2±0.32 µg m−3 and −4.6±0.88 ppb, respectively (changes quoted here are for the entire 2015–2055 time period; uncertainty represents the 95 % confidence interval), over global land surfaces, with larger reductions in some regions including south and southeast Asia. Non-methane NTCF mitigation, however, leads to additional climate change due to the removal of aerosol which causes a net warming effect, including global mean surface temperature and precipitation increases of 0.25±0.12 K and 0.03±0.012 mm d−1, respectively. Similarly, increases in extreme weather indices, including the hottest and wettest days, also occur. Regionally, the largest warming and wetting occurs over Asia, including central and north Asia (0.66±0.20 K and 0.03±0.02 mm d−1), south Asia (0.47±0.16 K and 0.17±0.09 mm d−1), and east Asia (0.46±0.20 K and 0.15±0.06 mm d−1). Relatively large warming and wetting of the Arctic also occur at 0.59±0.36 K and 0.04±0.02 mm d−1, respectively. Similar surface warming occurs in model simulations with aerosol-only mitigation, implying weak cooling due to ozone reductions. Our findings suggest that future policies that aggressively target non-methane NTCF reductions will improve air quality but will lead to additional surface warming, particularly in Asia and the Arctic. Policies that address other NTCFs including methane, as well as carbon dioxide emissions, must also be adopted to meet climate mitigation goals.

Climate↗

NASA NTRS2022

Gulf of Mexico Health & Air Quality Ii: Mapping Methane Emission Plumes Using Sunglint-Configured Imagery for Monitoring Offshore Oil and Gas Activity

Offshore oil and gas production in the United States is a major source of anthropogenic greenhouse gas emissions and accounts for nearly 30% of global oil and gas production. Methane venting and flaring are primary contributors to offshore emissions, and monitoring these activities is crucial for mitigating greenhouse gas emissions. Limited ground truthing and intermittent offshore satellite revisits make monitoring venting and flaring challenging. The Bureau of Ocean Energy Management (BOEM) and the Bureau of Safety and Environmental Enforcement (BSEE) oversee offshore oil and gas activity but rely primarily on operator-reported data. The non-profit organization SkyTruth monitors natural resources like methane and identifies sources of fugitive emissions. By combining BOEM and BSEE’s operational data along with observations from Sentinel-2 Multispectral Instrument (MSI), Landsat 8 Operational Land Imager (OLI) and Landsat 9 OLI-2, and PRecursore IperSpettrale della Missione Applicativa (PRISMA), the team further identified ultra-emitter point sources in the Gulf of Mexico using sunglint-configured imagery. We quantified these plume emission rates using the methodology from Varon et al. (2020). The team found three plumes in the Gulf of Mexico occurring between 2020 and 2022 using Sentinel-2 MSI and Landsat 9 OLI-2 imagery, in addition to the single plume identified by the Gulf of Mexico Health & Air Quality I team, and successfully quantified three plumes. Our statistical retrieval of three PRISMA images tasked over areas of interest yielded no methane plumes, despite a successful test of a known plume in Assam, India. These analyses serve as a proof of concept for the utility of remote sensing for methane emission monitoring offshore, which can complement regulator emission inventories and validate self-reported operator records.

sunglint↗

DOE OSTI2015

Transient seafloor venting on continental slopes from warming‐induced methane hydrate dissociation

Methane held in frozen hydrate cages within marine sediment comprises one of the largest carbon reservoirs on the planet. Recent submarine observations of widespread methane seepage may record hydrate dissociation due to oceanic warming, which consequently may further amplify climate change. Here, in this work, we simulate the effect of seafloor warming on marine hydrate deposits using a multiphase flow model. We show that hydrate dissociation, gas migration, and subsequent hydrate formation can generate temporary methane venting into the ocean through the hydrate stability zone. Methane seeps venting through the hydrate stability zone on the eastern Atlantic margin may record this process due to warming begun thousands of years ago. Our results contrast with the traditional view that venting occurs only updip of the hydrate stability zone.

hydrate↗

DOE OSTI2017

From Active-Site Models to Real Catalysts: Importance of the Material Gap in the Design of Pd Catalysts for Methane Oxidation

Rapid computational screening to aid novel catalyst design has evolved into an important and ubiquitous tool in modern heterogeneous catalysis. A possible shortcoming of this approach, however, is the material gap, that is, simplified computational models used for catalyst screening do not always capture the complexity of real catalytic systems. Here we investigate the importance of the material gap for complete methane oxidation over supported Pd/γ-Al2O3 catalysts using a combination of DFT simulations and temperature-programmed oxidation experiments. The Pd/γ-Al 2 O 3 active site was approximated by four models of increasing complexity, namely Pd(1 0 0), Pd(2 1 1), PdO(1 0 1), and Pd10/γ-Al 2 O 3 (1 1 0), and each was also modified with metal promoters to discover reactivity trends. Although the unpromoted Pd model surfaces exhibit different methane activation activities, our DFT results indicate that an experimentally verified performance trend can be predicted for their promoted counterparts irrespective of the active-site representation. We attribute the robustness of the trend predictions in this particular system to localized changes in the electron density during methane activation. Overall, our work supports the commonly practiced active-site model simplifications during computational catalyst screening and provides fundamental insight into the qualitative agreement between theory and experiment for methane oxidation over promoted Pd catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Thermodynamic Limitations of the Catalyst Design Space for Methanol Production from Methane

Current efforts to overcome the challenges of direct methane to methanol processes have focused on designing heterogeneous catalysts that perform methane partial oxidation using cheap and abundant oxidants such as molecular oxygen and water. An evaluation of the thermodynamic limitations of methanol production with the use of these oxidants is required to understand the maximum possible conversion and selectivity for a given feed composition and temperature. When O2 is present, the formation of the most thermodynamically stable product, carbon dioxide, must be inhibited. At practical temperatures for moderate scale processes, water as the sole oxidant results in extremely low steady-state methane conversion, but higher yields can be achieved with coupled surface reactions. This work evaluates these thermodynamic challenges and opportunities for catalysts that can selectively oxidize methane to methanol with oxygen and water and discusses routes for achieving high methanol yields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Methane Diffusion and Adsorption in Shale Rocks: A Numerical Study Using the Dusty Gas Model in TOUGH2/EOS7C-ECBM

Gas production from shale gas reservoirs plays a significant role in satisfying increasing energy demands. Compared with conventional sandstone and carbonate reservoirs, shale gas reservoirs are characterized by extremely low porosity, ultra-low permeability and high clay content. Slip flow, diffusion, adsorption and desorption are the primary gas transport processes in shale matrix, while Darcy flow is restricted to fractures. Understanding methane diffusion and adsorption, and gas flow and equilibrium in the low-permeability matrix of shale is crucial for shale formation evaluation and for predicting gas production. Modeling of diffusion in low-permeability shale rocks requires use of the Dusty gas model (DGM) rather than Fick’s law. The DGM is incorporated in the TOUGH2 module EOS7C-ECBM, a modified version of EOS7C that simulates multicomponent gas mixture transport in porous media. Also included in EOS7C-ECBM is the extended Langmuir model for adsorption and desorption of gases. In this study, a column shale model was constructed to simulate methane diffusion and adsorption through shale rocks. The process of binary CH 4 - N 2 diffusion and adsorption was analyzed. A sensitivity study was performed to investigate the effects of pressure, temperature and permeability on diffusion and adsorption in shale rocks. The results show that methane gas diffusion and adsorption in shale is a slow process of dynamic equilibrium, which can be illustrated by the slope of a curve in CH4mass variation. The amount of adsorption increases with the pressure increase at the low pressure, and the mass change by gas diffusion will decrease due to the decrease in the compressibility factor of the gas. With the elevated temperature, the gas molecules move faster and then the greater gas diffusion rates make the process duration shorter. The gas diffusion rate decreases with the permeability decrease, and there is a limit of gas diffusion if the permeability is less than 1.0×10 -15 m 2 . In conclusion, the results can provide insights for a better understanding of methane diffusion and adsorption in the shale rocks so as to optimize gas production performance of shale gas reservoirs.

04 OIL SHALES AND TAR SANDS↗

DOE OSTI2022

Enhancing methane production of anaerobic digested sewage sludge by advanced wet oxidation & steam explosion pretreatment

Anaerobic digestion (AD) of sewage sludge is associated with lowered carbon conversion efficiency due to the recalcitrance of microbial cells in the Waste Activated Sludge (WAS) from the aeration basins with 50 % of the dry weight still being present after AD. The effect of Advanced Wet Oxidation & Steam Explosion (AWOEx) pretreatment on the methane yield at variable temperatures (165–200 °C), residence time (15–45 min) and oxygen dosage (1%–10% based on VS concentration) was tested in this study. Central composite design (JMP® Pro) was used to design 19 runs of AWOEx pretreatment of dewatered digested sewage sludge (DADSS) at different operating conditions. After pretreatment the DADSS was fed to 19 bioreactors operated in semi-continues mode at 37 °C. The highest average methane yields of 183 mL/g VS and 170 mL/g VS were found for the bioreactors receiving DADSS pretreated at 165 °C with a retention time of 15 min and 10 % O2 (Condition 1), and, 182.5 °C with a retention time of 15 min and 5.5 % O2 (Condition 2). This corresponds to an increase in the methane production of 156.2 % and 140.5 % compared to the methane production from the DADSS without pretreatment.

09 BIOMASS FUELS↗

DOE OSTI2021

Dynamic in situ imaging of methane hydrate formation in coal media

Fast 3D X-ray imaging has proved to provide crucial insights into multi-phase dynamic processes in various geomaterials. In particular, many in situ imaging experiments have been made to study gas-hydrate formation in porous sandy samples. Such imaging is challenging for the methane gas-hydrate formation in coal samples because of the coal micro-porosity structure and lower X-ray contrast. Here we present results of the first dynamic in situ micro-computed tomography experiment of methane-hydrate formation in coal samples. Synchrotron phase-contrast tomography techniques allowed to achieve necessary contrast levels to separate all the materials of interest (gas, water, coal, and gas hydrate) in reconstructed images with high spatial and temporal resolution. The imaging results are compared to the ones from a similar tomographic experiment with sand samples. Methane-hydrate formation is accompanied by the water movements caused by cryogenic water suction that happens in sequences of short fast movements with longer equilibrium states in between. Only one type of the hydrate formation was observed in coal (growth as shells on grain boundaries) as opposed to three types in sand (shells, growth into gas pockets, and inside water volumes). In particular, this leads to a slower hydrateformation speed in coal. For the coal sample, we also observed water extraction from grains, and interpreted it as competitive sorption of methane. Lastly, we visualized the dynamic behavior of this water extraction via microchannels inside the coal grains, and performed nano-tomography imaging of these channels for a better understanding of this phenomenon.

58 GEOSCIENCES↗

DOE OSTI2018

Evaluation of getters for methane and ammonia decomposition

Getters are used in many tritium purification systems for impurity removal. One getter material, SAES® ST909, can be used to decompose various impurities (methane, carbon oxides, ammonia and others), and release the hydrogen bound in these compounds for further processing. Because, ST909 absorbs eight to nine percent of its initial weight in nitrogen, alternate materials may provide greater operational flexibility to accommodate variable operating carrier gases. The gettering capability of ST909 is related to the tri-metallic alloy (zirconium, manganese, and iron) composition. However, simply using a material with the same composition may not provide similar methane and ammonia decomposition conversion efficiency. For this testing, alternative materials to ST909 are compared to track methane and ammonia decomposition performance. Bench scale tests were performed at elevated temperature using various gas mixtures. Changes in methane and ammonia decomposition performance were tracked using RGA analysis during bench scale testing. Analytical comparisons of chemically equivalent materials to ST909 were also performed and correlated to bench scale test results. Characterization testing performed to evaluate chemically equivalent materials included: X-ray fluorescence, X-ray diffraction, and inductively coupled plasma-mass spectrometry (ICP-MS). Results are expounded upon and differences in gettering capability of alternate materials are highlighted.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

DOE OSTI2024

Compact and accurate chemical mechanism for methane pyrolysis with PAH growth

In this study, a reliable and compact chemical mechanism of gas-phase methane pyrolysis leading to formation of large polycyclic aromatic hydrocarbon (PAH) molecules has been developed. This model is designed for studies of carbon nanostructure synthesis such as carbon black and graphene flakes, including soot growth kinetics. Methane pyrolysis with carbon nanostructure synthesis is a two-stage process where conversion of CH 4 to C 2 H 2 precedes the growth of PAH molecules from acetylene. We present a single chemical mechanism that accurately describes both stages. We have constructed a compact and accurate chemical mechanism capable of modeling both stages of methane pyrolysis based on the ABF mechanism which was expanded with the most prominent reaction pathways from the mechanism by Tao for small PAH molecules and HACA pathways for larger PAH molecules, up to 37 aromatic rings. The resulting mechanism was validated through comparison to multiple available sets of experimental data. Good agreement with the experimental data for both processes was obtained. Performance of the mechanism was tested for pyrolysis of methane-rich mixtures under long residence times leading to abundant formation of PAH molecules. It is shown that the inclusion of larger PAH species (up to A37) in the chemical mechanism is important for accurate prediction of the fraction of carbon converted to PAH molecules and, correspondingly, the residual fraction of acetylene in the mixture. The mechanism file is available upon request.

08 HYDROGEN↗

DOE OSTI2017

High temperature infrared absorption cross sections of methane near 3.4 µm in Ar and CO 2 mixtures

In this study, the absorption cross-sections of CH 4 at two wavelengths in the mid-IR region: λ peak = 3403.4 nm and λ valley = 3403.7 nm were measured. Data were taken using three different compositions of non-reactive gas mixtures comprising CH 4 /Ar/CO 2 between 700 < T < 2000 K and 0.1 < P < 1.5 atm in a shock tube utilizing a continuous-wave distributed-feedback quantum cascade laser. Also, broadband room temperature methane cross section measurements were performed using a Fourier transform infrared spectrometer and the cascade laser to gain a better insight into the changes of the line shapes in various bath gasses (Ar, CO 2 , and N 2 ). An application of the high-temperature cross-section data was demonstrated to determine the concentration of methane during oxy-methane combustion in a mixture of CO 2 , O 2 , and Ar. Lastly, current measurements will be valuable addition to the spectroscopy database for methane- an important fuel used for power generation and heating around the world.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2013

Microbial distributions detected by an oligonucleotide microarray across geochemical zones associated with methane in marine sediments from the Ulleung Basin

The biogeochemical processes that occur in marine sediments on continental margins are complex; however, from one perspective they can be considered with respect to three geochemical zones based on the presence and form of methane: sulfate–methane transition (SMTZ), gas hydrate stability zone (GHSZ), and free gas zone (FGZ). These geochemical zones may harbor distinct microbial communities that are important in biogeochemical carbon cycles. The objective of this study was to describe the microbial communities in sediments from the SMTZ, GHSZ, and FGZ using molecular ecology methods (i.e. PhyloChip microarray analysis and terminal restriction fragment length polymorphism (T-RFLP)) and examining the results in the context of non-biological parameters in the sediments. Non-metric multidimensional scaling and multi-response permutation procedures were used to determine whether microbial community compositions were significantly different in the three geochemical zones and to correlate samples with abiotic characteristics of the sediments. This analysis indicated that microbial communities from all three zones were distinct from one another and that variables such as sulfate concentration, hydrate saturation of the nearest gas hydrate layer, and depth (or unmeasured variables associated with depth e.g. temperature, pressure) were correlated to differences between the three zones. The archaeal anaerobic methanotrophs typically attributed to performing anaerobic oxidation of methane were not detected in the SMTZ; however, the marine benthic group-B, which is often found in SMTZ, was detected. Within the GHSZ, samples that were typically closer to layers that contained higher hydrate saturation had indicator sequences related to Vibrio-type taxa. These results suggest that the biogeographic patterns of microbial communities in marine sediments are distinct based on geochemical zones defined by methane.

03 NATURAL GAS↗

DOE OSTI2017

Flux balance analysis indicates that methane is the lowest cost feedstock for microbial cell factories

The low cost of natural gas has driven significant interest in using C 1 carbon sources (e.g. methane, methanol, CO, syngas) as feedstocks for producing liquid transportation fuels and commodity chemicals. Given the large contribution of sugar and lignocellulosic feedstocks to biorefinery operating costs, natural gas and other C 1 sources may provide an economic advantage. To assess the relative costs of these feedstocks, we performed flux balance analysis on genome-scale metabolic models to calculate the maximum theoretical yields of chemical products from methane, methanol, acetate, and glucose. Yield calculations were performed for every metabolite (as a proxy for desired products) in the genome-scale metabolic models of three organisms: Escherichia coli (bacterium), Saccharomyces cerevisiae (yeast), and Synechococcus sp. PCC 7002 (cyanobacterium). The calculated theoretical yields and current feedstock prices provided inputs to create comparative feedstock cost surfaces. Our analysis shows that, at current market prices, methane feedstock costs are consistently lower than glucose when used as a carbon and energy source for microbial chemical production. Conversely, methanol is costlier than glucose under almost all price scenarios. Acetate feedstock costs could be less than glucose given efficient acetate production from low-cost syngas using nascent biological gas to liquids (BIO-GTL) technologies. Furthermore, our analysis suggests that research should focus on overcoming the technical challenges of methane assimilation and/or yield of acetate via BIO-GTL to take advantage of low-cost natural gas rather than using methanol as a feedstock.

09 BIOMASS FUELS↗

DOE OSTI2015

Enzymatic Oxidation of Methane

Methane monooxygenases (MMOs) are enzymes that catalyze the oxidation of methane to methanol in methanotrophic bacteria. As potential targets for new gas-to-liquid methane bioconversion processes, MMOs have attracted intense attention in recent years. There are two distinct types of MMO, a soluble, cytoplasmic MMO (sMMO) and a membrane-bound, particulate MMO (pMMO). Both oxidize methane at metal centers within a complex, multisubunit scaffold, but the structures, active sites, and chemical mechanisms are completely different. This Current Topic review article focuses on the overall architectures, active site structures, substrate reactivities, proteinprotein interactions, and chemical mechanisms of both MMOs, with an emphasis on fundamental aspects. In addition, recent advances, including new details of interactions between the sMMO components, characterization of sMMO intermediates, and progress toward understanding the pMMO metal centers are highlighted. The work summarized here provides a guide for those interested in exploiting MMOs for biotechnological applications.

Sirajuddin, S↗

DOE OSTI2025

Noble-Metal-Free, Nickel-Based Dual Functional Materials for Improved Methane Production from In Situ Carbon Dioxide Capture and Conversion

Promoters for dual functional materials have not been well explored, but promoters could improve the efficiency of the process by improving the selectivity of the CO 2 methanation process. Utilizing integrated capture and conversion, where CO 2 is captured and converted to useful products, would allow for a useful avenue to control CO 2 emissions. One such way to accomplish this would be to utilize materials that can both capture and convert CO 2 to useful products. However, these materials are often based on costly noble metals, like ruthenium and platinum, decreasing their viability on an industrial scale. Less expensive metals, for example, nickel, would allow for dual functional materials to be more readily utilized in industrial settings. Nickel-based dual functional materials often do not react with the captured CO 2 and merely desorb the CO 2 rather than form a useful product. However, promoters have not been well explored for these types of materials to improve the catalytic properties, which would be beneficial to improve nickel-based materials. Herein, we report the addition of ytterbium on a nickel-based dual functional material and the improvements to the production of methane from captured CO 2 with the incorporated ytterbium promoter. The ytterbium promoter improves the selectivity of the catalysts for the hydrogenation of captured CO 2 to methane and increases the ability for the material to capture CO 2 due to additional basic sites being formed on the surface of alumina. As a result, the 12%Ni/4%Yb/6%Na 2 O/Al 2 O 3 catalyst was utilized to capture carbon dioxide and then convert the captured CO 2 to methane over five cycles, where both the amount captured and the amount converted remained stable, indicating the stability of the material over long-term use.

Catalysts↗

DOE OSTI2019

Interaction of Methane with Calcium Ferrite in the Chemical Looping Partial Oxidation Application: Experimental and DFT Study

In this study, experimental studies using mass spectroscopy, thermogravimetric analysis, in situ X-ray diffraction (XRD), and theoretical density functional theory calculations were carried out to investigate the mechanism of methane partial oxidation over a CaFe 2 O 4 oxygen carrier. The XRD analysis revealed the formation of the calcium ferrite phases during methane reduction occurred in the sequence CaFe 2 O 4 →CaFe 3 O 5 + Ca 2 Fe 2 O 5 →FeO + Fe + CaO→Fe + CaO. Each of these phases was modeled using periodic density functional theory to study the activity of these phases for the reactivity with CH 4 , CO, and H 2 along with the adsorbed surface species to help elucidate the effect that phase changes during reduction have on the chemical looping products CO and H 2 . Mass spectroscopic analysis revealed the formation of H 2 O and CO 2 occurred prior to the formation of CO and H 2 , and these products may be due to the removal of lattice oxygen bound in the discrete primary phase, which contributes to a small portion (~16%) of the total transferable oxygen in the solid. The density functional theory (DFT) results suggest that the gaseous CO and H 2 are not thermodynamically favorable to react with the Ca 2 Fe 2 O 5 where the release of CO and H 2 led to an increase in selectivity for these products. The DFT results suggest that some of the adsorbed atomic hydrogen combined to form adsorbed H 2 and then gaseous H 2 on the CaFe 2 O 4 surface, while the carbon deposition and some adsorbed atomic hydrogen react to form the CaFe 3 O 5 and Ca 2 Fe 2 O 5 phases simultaneously. DFT simulations suggest that both the gaseous H 2 and adsorbed atomic H are less thermodynamically favorable to drive the deep reduction of Ca 2 Fe 2 O 5 to CaO and Fe0. The deep reduction of the calcium ferrite therefore favors the generation of syngas products (CO and H 2 ) through mechanisms of methane dehydrogenation and selective oxidation of carbon to CO. The significant difference in mechanisms for partial oxidation of methane to syngas with the CaFe 2 O 4 carrier can be correlated to the differences in the oxide phases present during the reduction process, concentration of oxygen species, and bonding in the lattice structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Evaluation of Nanaerobic Digestion as a Mechanism to Explain Surplus Methane Production in Animal Rumina and Engineered Digesters

Nanaerobes are a newly described class of microorganisms that use a unique cytochrome bd oxidase to achieve nanaerobic respiration at <2 μM dissolved oxygen (~1% of atmospheric oxygen) but are not viable above this value due to the lack of other terminal oxidases. Although sharing an overlapping ecological niche with methanogenic archaea, the role of nanaerobes in methanogenic systems has not been studied so far. To explore their occurrence and significance, we re-analyzed published meta-omic datasets from animal rumina and waste-to-energy digesters, including conventional anaerobic digesters and anaerobic digesters with ultra-low oxygenation. Results show that animal rumina share broad similarities in the microbial community and system performance with oxygenated digesters, rather than with conventional anaerobic digesters, implying that trace levels of oxygen drive the efficient digestion in ruminants. The rumen system serves as an ideal model for the newly named nanaerobic digestion, as it relies on the synergistic co-occurrence of nanaerobes and methanogens for methane yield enhancement. The most abundant ruminal bacterial family Prevotellaceae contains many nanaerobes, which perform not only anaerobic fermentation but also nanaerobic respiration using cytochrome bd oxidase. These nanaerobes generally accompany hydrogenotrophic methanogens to constitute a thermodynamically and physiologically consistent framework for efficient methane generation. Our findings provide new insights into ruminal methane emissions and strategies to enhance methane generation from biomass.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2025

Theoretical and Experimental Insights into CO 2 Capture and Methanation over Amine-Grafted Ru-Based Catalysts

Carbon capture and storage (CCS) technologies, along with CO 2 capture and conversion methods, have emerged as crucial research areas to address rising CO 2 emissions. In this study, we seek to understand the mechanistic role of amines in enabling lower-energy pathways for CO 2 conversion. Our research focuses on the development and analysis of dual-functional materials (DFMs) engineered for the reactive capture and conversion (RCC) of CO 2 into methane, utilizing Ru catalysts grafted with amine groups. We employ Density Functional Theory (DFT) calculations using methylamine as a model amine to investigate the impact of amine groups on CO 2 methanation on a Ru(0001) surface, both in the presence and absence of amine groups. The amine ligand alters the carbon coordination environment, promoting direct C–O dissociation and potentially destabilizing the CO* adsorbate, thereby reducing the risk of CO poisoning. Additionally, we observe a preference for hydrogenation, although it becomes more energetically uphill in the amine-bound scenario. Our experiments, however, report similar CO 2 conversion and CH 4 production rates over the synthesized catalysts “Ru/TiO 2 ” and the amine (N-(2-aminoethyl)-3-aminoproplytrimethoxysilane (“diaminosilane”)) deposited catalyst “Diamine−Ru/TiO 2 ”. By constructing comparative reaction-free energy diagrams and performing microkinetic modeling (MKM) simulations, we link our theoretical findings with experimentally observed CO 2 uptake, conversion, and methane production rates. A microkinetic model was employed to investigate the anomaly, showing reduced amine–carbon complex coverage and increased CO 2 coverage at all temperatures. The MKM simulations consistently confirmed these trends. In conclusion, this comprehensive approach offers key insights into the role of the amine-CO 2 bond in methanation, highlighting a pathway toward lower-energy, more efficient CO 2 capture and conversion processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗