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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Active Palladium Structures on Ceria Obtained by Tuning Pd–Pd Distance for Efficient Methane Combustion

Efficiently removing/converting methane via methane combustion imposes challenges on catalyst design: how to design local structures of a catalytic site so that it has both high intrinsic activity and atomic efficiency? By manipulating the atomic distance of isolated Pd atoms, herein we show that the intrinsic activity of Pd catalysts can be significantly improved for methane combustion via a stable Pd 2 structure on a ceria nanorod support. Guided by theory and confirmed by experiment, we find that the turnover frequency (TOF) of the Pd 2 structure with the Pd–Pd distance of 2.99 Å is higher than that of the Pd 2 structure with the Pd–Pd distance of 2.75 Å; at least 26 times that of ceria supported Pd single atoms and 4 times that of ceria supported PdO nanoparticles. The high intrinsic activity of the 2.99 Å Pd–Pd structure is attributed to the conductive local redox environment from the two O atoms bridging the two Pd 2+ ions, which facilitates both methane adsorption and activation as well as the production of water and carbon dioxide during the methane oxidation process. In conclusion, this work highlights the sensitivity of catalytic behavior on the local structure of active sites and the fine-tuning of the metal–metal distance enabled by a support local environment for guiding the design of efficient catalysts for reactions that highly rely on Pt-group metals.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Automatic detection of methane emissions in multispectral satellite imagery using a vision transformer

Curbing methane emissions is among the most effective actions that can be taken to slow down global warming. However, monitoring emissions remains challenging, as detection methods have a limited quantification completeness due to trade-offs that have to be made between coverage, resolution and detection accuracy. Here we show that deep learning can overcome the trade-off in terms of spectral resolution that comes with multi-spectral satellite data, resulting in a methane detection tool with global coverage and high temporal and spatial resolution. We compare our detections with airborne methane measurement campaigns, which suggests that our method can detect methane point sources in Sentinel-2 data down to plumes of 0.01 km 2 , corresponding to 200 to 300 kg CH 4 /h -1 sources. Our model shows an order of magnitude improvement over the state-of-the-art, providing a significant step towards the automated, high resolution detection of methane emissions at a global scale, every few days.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Surface characterization and methane activation on SnO x /Cu 2 O/Cu(111) inverse oxide/metal catalysts

To activate methane at low or medium temperatures is a difficult task and a pre-requisite for the conversion of this light alkane into high value chemicals. In this work, we report the preparation and characterizations of novel SnO x /Cu 2 O/Cu(111) interfaces that enable low-temperature methane activation. Scanning tunneling microscopy identified small, well-dispersed SnO x nanoclusters on the Cu 2 O/Cu(111) substrate with an average size of 8 Å, and such morphology was sustained up to 450 K in UHV annealing. Ambient pressure X-ray photoelectron spectroscopy showed that hydrocarbon species (CH x groups), the product of methane activation, were formed on SnO x /Cu 2 O/Cu(111) at a temperature as low as 300 K. An essential role of the SnO x –Cu 2 O interface was evinced by the SnO x coverage dependence. Systems with a small amount of tin oxide, 0.1–0.2 ML coverage, produced the highest concentration of adsorbed CH x groups. Calculations based on density functional theory showed a drastic reduction in the activation barrier for C–H bond cleavage when going from Cu 2 O/Cu(111) to SnO x /Cu 2 O/Cu(111). On the supported SnO x , the dissociation of methane was highly exothermic (ΔE ~ –35 kcal mol –1 ) and the calculated barrier for activation (~20 kcal mol –1 ) could be overcome at 300–500 K, target temperatures for the conversion of methane to high value chemicals.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Assessing the design of integrated methane sensing networks

Abstract While methane is the second largest contributor to global warming after carbon dioxide, it has a larger warming effect over a much shorter lifetime. Despite accelerated technological efforts to radically reduce global carbon dioxide emissions, rapid reductions in methane emissions are needed to limit near-term warming. Being primarily emitted as a byproduct from agricultural activities and energy extraction, methane is currently monitored via bottom–up (i.e. activity level) or top–down (via airborne or satellite retrievals) approaches. However, significant methane leaks remain undetected and emission rates are challenging to characterize with current monitoring frameworks. In this paper, we study the design of a layered monitoring approach that combines bottom–up and top–down approaches as an integrated sensing network. By recognizing that varying meteorological conditions and emission rates impact the efficacy of bottom–up monitoring, we develop a probabilistic approach to optimal sensor placement in its bottom–up network. Subsequently, we derive an inverse Bayesian framework to quantify the improvement that a design-optimized integrated framework has on emission-rate quantifications and their uncertainties. We find that under realistic meteorological conditions, the overall error in estimating the true emission rates is approximately 1.3 times higher, with their uncertainties being approximately 2.4 times higher, when using a randomized network over an optimized network, highlighting the importance of optimizing the design of integrated methane sensing networks. Further, we find that optimized networks can improve scenario coverage fractions by more than a factor of 2 over experimentally-studied networks, and identify a budget threshold beyond which the rate of optimized-network coverage improvement exhibits diminishing returns, suggesting that strategic sensor placement is also crucial for maximizing network efficiency.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Systems Level Understanding of Interconnected Methane and Nitrogen Cycles Using Complex Synthetic Communities

The main goal of this project was to follow up on prior discovery of the communal nature of methane utilization by the aerobic methanotrophic bacteria, resulting in carbon transfer along a food chain. This goal was approached via manipulation of specially designed, synthetic bacterial communities, fed exclusively by methane, under a variety of simulated environmental conditions. Using (meta)genomics, metatranscriptomics, stable isotope probing and mutant generation, we obtained solid evidence for the nature of the core microbiota involved in collaborative methane consumption, the major players (true methanotrophs) being the members of the family Methylococcaceae, their major partners (non-methanotrophic methylotrophs) being members of the family Methylophilaceae, and minor but persistent partners in the communities being members of the orders Burkholderiales and Bacteroidetes. Metabolic reconstruction from single genomes and metagenome-assembled genomes (MAGs), along with metatranscriptomics results delineated major pathways for carbon metabolism, suggesting that the methanotrophs share different organic compounds with different functional guilds: methanol with Methylophilaceae, acetate with Burkholderiales, and polymeric substances with Bacteroidetes. Overall, the results of this project expand our understanding of microbial metabolism of methane and, thus, provide basis for strategies for microbial methane mitigation, with obvious benefits to the society of the United States and worldwide.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Frequency Comb-Based Remote Methane Observation Network (Final Scientific/Technical Report)

ARPA-E investment in long-range, frequency comb-based methane detection has resulted in the first scalable, cost-effective continuous methane emissions system. At the onset of this ARPA-E MONITOR award, the dual-frequency comb spectrometer was a sprawling, expensive, laboratory-confined device which had only recently been demonstrated capable of measuring atmospheric trace gases over open-paths. Bringing the technology to the point of being able to monitor for and characterize methane emissions at oil and natural gas production facilities seemed an almost impossible task. Over the subsequent months and years, our team transitioned the Nobel-prize-winning frequency-comb-laser spectrometer technology to a field-deployed regional methane leak detection system. The spectrometer enables highly sensitive near-infrared absorption measurements of methane along kilometer-scale laser beam paths. The measurements are coupled with an atmospheric modeling and inversion framework to triangulate the location of emission sources and quantify the emission rates.

03 NATURAL GAS↗
DOE OSTI2023

Methane Partial Oxidation over Multifunctional 2-D Materials

The objective of this research is to design, synthesize, and evaluate highly selective, active, and stable multifunctional catalysts for the low temperature (< 500 Kelvin (K)) partial oxidation of methane to methanol (MTM) with molecular oxygen: CH 4 (g) + $\frac{1}{2}$O 2 (g) → CH 3 OH(g). Methane, the primary component of natural gas, is a source of energy and economic growth as well as an environmental concern. Recent developments in horizontal drilling and enhanced extraction methods have resulted in production of an estimated 62.4 trillion m 3 of ‘stranded’, or uneconomic, natural gas. Uneconomical natural gas is often flared or vented at remote oil production sites. Leaked, flared, and/or vented gas represents a "lost opportunity”, and this research project aims to maximize the value of the resource. Conventional catalysts for MTM suffer from low methanol selectivity since they exhibit ~0.55 eV higher barrier for C-H bond activation of methane compared to methanol. Without breaking these scaling relations, methanol oxidation is orders of magnitude faster than methane oxidation and it is very challenging to envision a process with economically viable single-pass yield. Here, we chose to investigate single-atom catalysts embedded and stabilized in two-dimensional materials such as graphene (GR) and "supported" on Group VIII and IB transition metals such as nickel. The electronic atomic monolayer-metal support interaction (EAMSI) present in these systems could promote methanol selectivity by breaking the scaling relations of the C-H bond activation of methane and methanol. A density functional theory (DFT) based computational study focused on predicting families of GR-based catalysts that could be active and selective for MTM. The catalyst systems predicted by the computational study were synthesized and evaluated for the gas phase MTM under relevant conditions. Unfortunately, the experimental activity and selectivity was lower than computationally predicted. The origin for the discrepancy is likely related to difficulties in synthesizing single atom catalysts in a threecomponent catalyst system at high density and with high selectivity. Future work in our groups is thus focused on reducing the system complexity to a two-component catalyst system. Finally, a techno-economic analysis (TEA) was also conducted to identify critical bottlenecks that inhibit future commercialization.

03 NATURAL GAS↗
DOE OSTI2025

Cell to Ecosystem: Understanding Methane and Associated Nutrient Cycling by Sediment Hosted Syntrophic Consortia and Their Viral Predators

The anaerobic oxidation of methane (AOM) is a significant worldwide microbial process in anoxic lake and ocean sediments, responsible for sequestering up to 80% of this greenhouse gas. Often considered a metabolism on the edge of thermodynamic probability, the impact of ANaerobic MEthane-oxidizing ‘ANME’ archaea on carbon and nutrient cycling in sediment ecosystems is far reaching. They not only serve as a sink for methane coupled to diverse electron acceptors, but also catalyze the transformation of many important nutrients including nitrogen, phosphate, and iron. While information about the potential mechanisms supporting metabolism in AOM is now available, remarkably little has been learned about their nutritional requirements, their dependencies on bacterial partners, and consequentially their ultimate impact on nutrient transformation and bioavailability within sedimentary ecosystems, and beyond. Further, the role of viruses within sediment ecosystems represents an essential but vastly understudied aspect of the transformation of carbon and nutrients by AOM. Viruses are now widely appreciated as central players in biogeochemical cycles across diverse ecosystems. These nanoscale predators have been shown to enhance the turnover of essential nutrients, thus stimulating microbial growth and environmental viruses themselves may constitute an important reservoir of nitrogen and phosphorous. Little is known about the role of viruses in methane-impacted sedimentary ecosystems, however prior genomic and microscopy evidence suggests that AOM consortia are susceptible to phage infection. The overarching scientific goal of this multi-disciplinary research proposal is to build on these recent discoveries and expand our understanding of interactions and fundamental activities involved in cycling of carbon and nutrients by syntrophic methanotrophic archaeal-bacterial consortia and associated viruses in anoxic sedimentary environments. Our three specific objectives are to 1) Quantify energy and nutrient exchange (e.g. N, P, Fe and vitamins) within AOM consortia and between ANME-bacterial partners; 2) Identify virus-host interactions associated with AOM and assess C and N transfer through viruses in methane-impacted sediment ecosystems; 3) Model energy and nutrient exchange in AOM consortia and viral-host interactions (i.e. viral activity), and their environmental distribution patterns. Our experimental emphasis cuts across scales that are important for understanding microbial and viral interactions and activities within their habitats, as well as community wide biogeochemical transformations. These research goals will be accomplished through the application of novel molecular techniques targeting DNA, RNA, proteins, and metabolites combined with a unique multi-modal analytical imaging pipeline. We will then model the ecophysiological capabilities of diverse sediment-hosted methanotrophic consortia to develop a more comprehensive understanding of the energetic and nutritional interactions between different AOM partner couplings that occur in sediments.

03 NATURAL GAS↗
DOE OSTI2025

Integrated System for Methane Emissions Monitoring, Mapping, and Quantification

This report presents the work completed under the DOE iM4 project for the development of a methane emission monitoring system for detection, location, and quantification of methane in oil and gas industries. The task was divided into four main areas including: 1) Sensors and Input, 2) Centralized Cloud Information Center, 3) Algorithms, and 4) Testing and Validation. Task 1 focused on researching and developing an understanding of the current, or soon to be, available methane sensing technologies. Task 2 consisted of developing the architecture, selecting hardware, software and elements for the methane monitoring system. Task 3 focused on the algorithms used for the complex inverse model of going from measured methane signatures to the detection, localization, and quantification of sources that are desired. Finally, Task 4 focused on the methods of testing and validating the operation of the system. Attention was also given to the development method and cost breakdown of the system.

03 NATURAL GAS↗
DOE OSTI2025

Reducing Methane Emissions with an Engine Fuel Reformer

Southwest Research Institute (SwRI) designed and demonstrated a compact, plasma-based fuel reformer designed to reduce methane leaks from natural-gas engines used in pipeline compression and industrial power applications. The system uses pulsed electrical discharges to convert a small portion of methane (CH4) into hydrogen (H2) and light hydrocarbons, promoting more complete combustion and reducing unburned methane in the exhaust. The reformer was evaluated through bench-scale testing, high-flow facility testing, and engine-integration testing on representative low-speed and high-speed natural-gas engines. Measured methane-leak reductions ranged from 1 to 27 percent, depending on engine type and operating condition, while reformer energy consumption remained below one percent of total engine output. Design refinements addressed thermal and electrical challenges, resulting in reliable operation with minimal impact on engine control systems. The project achieved all performance objectives within budget and schedule, produced a patentable pulsed-power system design, and established a scalable, energy-efficient pathway for mitigating methane leaks from existing natural-gas engine infrastructure.

03 NATURAL GAS↗
DOE OSTI2024

Estimating Total Methane Emissions from the Denver-Julesburg Basin Using Bottom-Up Approaches

Methane is a powerful greenhouse gas with a 25 times higher 100-year warming potential than carbon dioxide and is a target for mitigation to achieve climate goals. To control and curb methane emissions, estimates are required from the sources and sectors which are typically generated using bottom-up methods. However, recent studies have shown that national and international bottom-up approaches can significantly underestimate emissions. In this study, we present three bottom-up approaches used to estimate methane emissions from all emission sectors in the Denver-Julesburg basin, CO, USA. Our data show emissions generated from all three methods are lower than historic measurements. A Tier 1/2 approach using IPCC emission factors estimated 2022 methane emissions of 358 Gg (0.8% of produced methane lost by the energy sector), while a Tier 3 EPA-based approach estimated emissions of 269 Gg (0.2%). Using emission factors informed by contemporary and region-specific measurement studies, emissions of 212 Gg (0.2%) were calculated. The largest difference in emissions estimates were a result of using the Mechanistic Air Emissions Simulator (MAES) for the production and transport of oil and gas in the DJ basin. The MAES accounts for changes to regulatory practice in the DJ basin, which include comprehensive requirements for compressors, pneumatics, equipment leaks, and fugitive emissions, which were implemented to reduce emissions starting in 2014. The measurement revealed that normalized gas loss is predicted to have been reduced by a factor of 20 when compared to 10-year-old normalization loss measurements and a factor of 10 less than a nearby oil and production area (Delaware basin, TX); however, we suggest that more measurements should be made to ensure that the long-tail emission distribution has been captured by the modeling. This study suggests that regulations implemented by the Colorado Department of Public Health and Environment could have reduced emissions by a factor of 20, but contemporary regional measurements should be made to ensure these bottom-up calculations are realistic.

03 NATURAL GAS↗
DOE OSTI2024

Quantifying Drivers of Methane Hydrobiogeochemistry in a Tidal River Floodplain System

The influence of coastal ecosystems on global greenhouse gas (GHG) budgets and their response to increasing inundation and salinization remains poorly constrained. In this study, we have integrated an uncertainty quantification (UQ) and ensemble machine learning (ML) framework to identify and rank the most influential processes, properties, and conditions controlling methane behavior in a freshwater floodplain responding to recently restored seawater inundation. Our unique multivariate, multiyear, and multi-site dataset comprises tidal creek and floodplain porewater observations encompassing water level, salinity, pH, temperature, dissolved oxygen (DO), dissolved organic carbon (DOC), total dissolved nitrogen (TDN), partial pressure of carbon dioxide (pCO 2 ), nitrous oxide (pN 2 O), methane (pCH 4 ), and the stable isotopic composition of methane (δ 13 CH 4 ). Additionally, we incorporated topographical data, soil porosity, hydraulic conductivity, and water retention parameters for UQ analysis using a previously developed 3D variably saturated flow and transport floodplain model for a physical mechanistic understanding of factors influencing groundwater levels and salinity and, therefore, CH 4 . Principal component analysis revealed that groundwater level and salinity are the most significant predictors of overall biogeochemical variability. The ensemble ML models and UQ analyses identified DO, water level, salinity, and temperature as the most influential factors for porewater methane levels and indicated that approximately 80% of the total variability in hourly water levels and around 60% of the total variability in hourly salinity can be explained by permeability, creek water level, and two van Genuchten water retention function parameters: the air-entry suction parameter α and the pore size distribution parameter m. These findings provide insights on the physicochemical factors in methane behavior in coastal ecosystems and their representation in local- to global-scale Earth system models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Development of Methane Emissions Model to Assess Fuel Recovery Potential at Gas Well Sites Using On Site Compression

The U.S. natural gas production and consumption has increased 85.5% since 2005 primarily due to the unconventional production methods of horizontal drilling and hydraulic fracturing. Natural gas used as a fuel has a lower greenhouse gas (GHG) footprint than coal and petroleum due to lower Carbon Dioxide (CO2) emissions when combusted. However, the “greener” benefit to natural gas may be negated by leaks in production and transmission systems. Methane (CH4), the primary hydrocarbon in natural gas, has an estimated Global Warming Potential (GWP) of 28-36 over 100 years, meaning it can absorb 28-36 more energy than CO2 which has a GWP of 1.0. Natural gas well sites are prone to methane emissions, or leaks and irregular gas releases, vented to atmosphere throughout production and transmission. The U.S. Department of Energy (DOE) and the National Energy Technology Laboratory (NETL) has recently granted West Virginia University (WVU) funding under agreement DE-FOA-0002005, to “Advance technologies to mitigate methane emissions and increase the efficiency of the natural gas transportation infrastructure”. As part of this funding WVU was tasked with identifying and quantifying sources of methane emissions at unconventional well sites, processing this data, and developing a system to recapture these emissions. A 0-D Simulink model was developed, utilizing standardized methodologies, data from previously conducted studies, as well as collected data from well sites in the Marcellus shale play region. The model was developed to predict emission rates from various components at natural gas well sites as well as the potential to utilize these emissions as fuel for the natural gas powered compressor engines on-site. This model was utilized to run high, medium, and low cases for four identified emission sources, engine size, pneumatic controller count, liquid level production which dictates tank emissions, and compressor packing vent emissions. Due to discrepancies in transient tank emission data, a high and low emission factor for tanks was used, resulting in two sets of 81 executed cases, and 162 unique cases of total site emissions and potential for fuel consumption. Each of the cases were run over 86,400 seconds at a 1 Hz, representative of a full 24 hour day of operation. The fuel consumption offset an average of 557% of fuel consumption on an energy density basis across all 81 cases with the high tank emission factor with a maximum offset of 2334%. The fuel consumption offset was an average of 82.9% for all 81 cases with the low tank emission factor with a maximum offset of 337%. This study highlights flaws in the use of publicly available methane number calculations to determine natural gas’s suitability as an engine fuel as well as the lack of public data for transient liquid storage tank emissions.

03 NATURAL GAS↗
DOE OSTI2026

A Global Methane Observation System to Reduce Uncertainty for Anthropogenic and Natural Sources and Sinks for Detecting and Attributing Climate Feedbacks

Atmospheric methane (CH4) concentrations are accelerating global warming as net emissions increase. Observing systems that quantify sources remain too sparse and fragmented to detect trends—especially in remote regions where climate‐driven natural emissions may be rising. We provide a framework for quantifying uncertainty reductions through the implementation of a global ecosystem‐methane observing system designed to: (i) substantially lower uncertainty in sectoral and regional emissions, (ii) separate co‐occurring anthropogenic and natural fluxes, and (iii) trend detection at regional scales to verify mitigation progress and provide early warning of natural feedbacks. Using bottom‐up inventories and process‐model ensembles for 2014–2023, we show that anthropogenic emissions remain uncertain by ∼32% globally, while natural sources—tropical and boreal‐arctic wetlands, fires, and inland waters—carry far larger uncertainties (+ 70%) and trend uncertainties reaching ∼200%. Additional observations must match spatial emission structure to increase observability of emissions: high‐resolution satellite constellations for point sources combined with expanded flux networks and wetland mapping for diffuse sources, and denser ground‐based atmospheric column measurements to restore observability in under‐sampled tropics and high latitudes. Notional analyses indicate that targeted additions of flux towers and ∼20 in situ atmospheric column concentration instruments per key tropical region could reduce continental‐scale uncertainties at modest cost. Conceptual illustration of a Global Ecosystem Methane Observing System (GEM‐OS) integrating satellites, aircraft, atmospheric networks, and ecosystem measurements to quantify methane emissions from anthropogenic and natural sources. The multi‐scale observing framework improves source attribution, reduces uncertainty in regional methane budgets, and enables early detection of climate‐driven feedbacks from wetlands, fires, permafrost, agriculture, and fossil‐fuel emissions.

Ciais, P↗
DOE OSTI2021

Role of redox-active biochar with distinctive electrochemical properties to promote methane production in anaerobic digestion of waste activated sludge

Biochar has been reported as an effective additive to improve methane production during anaerobic digestion (AD). However, the mechanism for such a stimulatory impact remains unclear. Here we investigated the capability of three pyrolytic biochars with distinctive electrochemical properties (BC300, BC500, BC700) to promote methanogenic performance of anaerobic digesters treating waste activated sludge (WAS). The cumulative methane production and the maximum methane production rate were increased by 46.9% and 181.6%, respectively, with BC300 amendment. By characterizing the electrochemical properties of biochar, our research team found out that methane production in AD of sludge was positively correlated to biochar’s electron-donating capacity (EDC) rather than its bulk electrical conductivity. These results indicate that the electron transfer mediated by the redox-active functional groups may prevail over the direct electron migration as the predominant mechanism to facilitate interspecies electron transfer in syntrophic communities for enhanced methanogenesis. Microbial community analysis suggests that biochar enriched Methanosarcina and Methanobacterium. Overall, this study shows that functional groups-mediated electron transfer contributes greatly to the improved methane production in WAS digester with biochar amendment.

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

Methane Generation from CO 2 with a Molecular Rhenium Catalyst

The atomic-level tunability of molecular structures is a compelling reason to develop homogeneous catalysts for challenging reactions such as the electrochemical reduction of carbon dioxide to valuable C 1 –C n products. Of particular interest is methane, the largest component of natural gas. Herein, we report a series of three isomeric rhenium tricarbonyl complexes coordinated by the asymmetric diimine ligands 2-(isoquinolin-1-yl)-4,5-dihydrooxazole ( quin-1-oxa ), 2-(quinolin-2-yl)-4,5-dihydrooxazole ( quin-2-oxa ), and 2-(isoquinolin-3-yl)-4,5-dihydrooxazole ( quin-3-oxa ) that catalyze the reduction of CO 2 to carbon monoxide and methane, albeit the latter with a low efficiency. To our knowledge, these complexes are the first examples of rhenium(I) catalysts capable of converting carbon dioxide into methane. Re(quin-1-oxa)(CO) 3 Cl ( 1 ), Re(quin-2-oxa)(CO) 3 Cl ( 2 ), and Re(quin-3-oxa)(CO) 3 Cl ( 3 ) were characterized and studied using a variety of electrochemical and spectroscopic techniques. In bulk electrolysis experiments, the three complexes reduce CO 2 to CO and CH 4 . When the controlled-potential electrolysis experiments are performed at -2.5 V (vs Fc +/0 ) and in the presence of the Brønsted acid 2,2,2-trifluoroethanol, methane is produced with turnover numbers that range from 1.3 to 1.8. Isotope labeling experiments using 13 CO 2 atmosphere produce 13 CH 4 ( m / z = 17) confirming that methane originates from CO 2 reduction. Theoretical calculations are performed to investigate the mechanistic aspects of the 8e – /8H + reduction of CO 2 to CH 4 . Overall, a ligand-assisted pathway is proposed to be an efficient pathway in the formation of CH 4 . Delocalization of the electron density on the (iso)quinoline moiety upon reduction stabilizes the key carbonyl intermediate leading to additional reactivity of this ligand. These results should aid the development of more robust catalytic systems that produce CH 4 from CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Plasma-Assisted Chemical-Looping Combustion: Low-Temperature Methane and Ethylene Oxidation with Nickel Oxide

The chemical reaction network of low-temperature plasma-assisted oxidation of methane (CH 4 ) and ethylene (C 2 H 4 ) with nickel oxide (NiO) was investigated in a heated plasma reactor through time-dependent species measurements by electron-ionization molecular beam mass spectrometry (EI-MBMS). Methane (ethylene) oxidation by NiO was explored in temperature ranges from 300-700 °C (300-500 °C) and 300-800 °C (300-600°C) for the plasma and non-plasma conditions, respectively. Significant enhancement of methane oxidation was observed with plasma between 400 and 500 °C, where no oxidation was observed under non-plasma conditions. For the oxidation of methane at higher temperatures three different oxidation stages were observed: I) a period of complete oxidation, II) a period of incomplete CO oxidation, and III) a period of carbon buildup. For the C 2 H 4 experiments, and unlike the CH 4 experiments, the plasma resulted in a significant amount of new intermediate oxygenated species, such as CH 2 O, CH 3 OH, C 2 H 4 O, and C 2 H 6 O. Carbon deposits were observed under both methane and ethylene conditions and verified by X-ray photoelectron spectroscopy (XPS). ReaxFF simulations were performed for the oxidation of CH 4 and C 2 H 4 in a non-plasma environment. The simulated intermediates and products largely agree with the species measured in the experiments, though the predicted intermediate oxygenated species such as CH 2 O and C 2 H 6 O were not observed in experiments under non-plasma conditions. A reaction pathway analysis for CH 4 and C 2 H 4 reacting with NiO was created based on the observed species from the MBMS spectra, along with ReaxFF simulations.

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

Screening of Cu-Based Catalysts for Selective Methane to Methanol Conversion

Developing selective catalysts for methane conversion to added value chemicals has been considered as a promising approach for efficient utilization of abundant natural gas resources. Here, we present a descriptor-based screening for high methane conversion and methanol selectivity at the interfaces between metal oxide clusters and Cu 2 O/Cu(111) support (MO x /Cu 2 O/Cu(111), M = Mg, Fe, Co, Ni, Cu, Zn, Ti, Zr, Sn, Ce) on exposure to the mixture of CH 4 /O 2 /H 2 O. Wherein, the activation energy of direct methane to methanol conversion, *OH + *CH 4 → *CH 3 OH + *H, and the ratio for adsorption energy of oxygen and water, E ads (O 2 )/E ads (H 2 O), are identified as the effective descriptor for methane conversion and methanol selectivity, respectively. Finally, by providing an exceptional oxygen and hydroxyl sites with high-lying O 2p states, the MgO/Cu 2 O/Cu(111) catalyst is found to be the most promising system among the systems studied, being able to provide the highest methane conversion with high methanol selectivity.

03 NATURAL GAS↗