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DOE OSTI2024

Low-Temperature Activation and Coupling of Methane on MgO Nanostructures Embedded in Cu 2 O/Cu(111)

Here, the efficient conversion of methane into valuable hydrocarbons such as ethane and ethylene at relatively low temperatures without deactivation issues is crucial for advancing sustainable energy solutions. Herein, AP-XPS and STM studies show that MgO nanostructures (0.2-0.5 nm wide, 0.4-0.6 Å high) embedded in a Cu 2 O/Cu(111) substrate activate methane at room temperature, mainly dissociating it into CH x (x = 2 or 3) and H adatoms, with minimal conversion to C adatoms. These MgO nanostructures in contact with Cu 2 O/Cu(111) exhibit unique reactivity, enabling C-C coupling into ethane and ethylene at 500 K, a significantly lower temperature than that required for bulk MgO catalysts (>700 K), with negligible carbon deposition and no deactivation. DFT calculations corroborate these experimental findings. The CH 4,gas → *CH 3 +*H reaction is a downhill process on MgO/Cu 2 O/Cu(111) surfaces. The activation of methane is facilitated by an electron transfer from copper to MgO and the existence of Mg and O atoms with a low coordination number in the oxide nanostructures. The formation of O-CH 3 and O-H bonds overcomes the energy necessary for the cleavage of a C-H bond in methane. DFT studies reveal that smaller Mg 2 O 2 model clusters provide stronger binding and lower activation barriers for C-H dissociation in CH 4 , while larger Mg 3 O 3 clusters promote C-C coupling due to weaker *CH 3 binding. All these results emphasize the importance of size when optimizing the catalytic performance of MgO nanostructures in the selective conversion of methane.

36 MATERIALS SCIENCE↗

DOE OSTI2017

Methane-Fueled Syntrophy through Extracellular Electron Transfer: Uncovering the Genomic Traits Conserved within Diverse Bacterial Partners of Anaerobic Methanotrophic Archaea

The anaerobic oxidation of methane by anaerobic methanotrophic (ANME) archaea in syntrophic partnership with deltaproteobacterial sulfate-reducing bacteria (SRB) is the primary mechanism for methane removal in ocean sediments. The mechanism of their syntrophy has been the subject of much research as traditional intermediate compounds, such as hydrogen and formate, failed to decouple the partners. Recent findings have indicated the potential for extracellular electron transfer from ANME archaea to SRB, though it is unclear how extracellular electrons are integrated into the metabolism of the SRB partner. We used metagenomics to reconstruct eight genomes from the globally distributed SEEP-SRB1 clade of ANME partner bacteria to determine what genomic features are required for syntrophy. The SEEP-SRB1 genomes contain large multiheme cytochromes that were not found in previously described free-living SRB and also lack periplasmic hydrogenases that may prevent an independent lifestyle without an extracellular source of electrons from ANME archaea. Metaproteomics revealed the expression of these cytochromes at in situ methane seep sediments from three sites along the Pacific coast of the United States. Phylogenetic analysis showed that these cytochromes appear to have been horizontally transferred from metal-respiring members of the Deltaproteobacteria such as Geobacter and may allow these syntrophic SRB to accept extracellular electrons in place of other chemical/organic electron donors. Some archaea, known as anaerobic methanotrophs, are capable of converting methane into carbon dioxide when they are growing syntopically with sulfate-reducing bacteria. This partnership is the primary mechanism for methane removal in ocean sediments; however, there is still much to learn about how this syntrophy works. Previous studies have failed to identify the metabolic intermediate, such as hydrogen or formate, that is passed between partners. However, recent analysis of methanotrophic archaea has suggested that the syntrophy is formed through direct electron transfer. In this research, we analyzed the genomes of multiple partner bacteria and showed that they also contain the genes necessary to perform extracellular electron transfer, which are absent in related bacteria that do not form syntrophic partnerships with anaerobic methanotrophs. This genomic evidence shows a possible mechanism for direct electron transfer from methanotrophic archaea into the metabolism of the partner bacteria.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2024

Integrated Methane Monitoring Platform Design (Final Report)

As the urgency for understanding methane emissions and the number of methane monitoring technologies being deployed have increased in the last two decades, there is an opportunity and a need to integrate the numerous disparate data sources to enable the detection, quantification, contextualization, and reporting of methane emissions along the oil and gas supply chain. Such an integration would enable emissions reductions through early detection of super emitters, data-driven mitigation strategies, and improved greenhouse gas inventories. The GTI Energy (“GTI”) project team (“the team”) worked with a multitude of industry experts, stakeholders, and subject matter experts (SMEs) to collect guidance, insights, and information to inform the requirements and subsequent engineering, design, deployment, and operations of an integrated methane monitoring platform (IMMP). This final report describes the results of the team’s effort to execute the Integrated Methane Monitoring Platform Design project, ultimately providing an engineering, design, deployment, and operating plan (EDDOP) for the IMMP. This final report summarizes and integrates the project tasks' results and outputs.

03 NATURAL GAS↗

DOE OSTI2024

Supporting Information for the Integrated Methane Monitoring Platform Design (Final Report)

As the urgency for understanding methane emissions and the number of methane monitoring technologies being deployed have increased in the last two decades, there is an opportunity and a need to integrate the numerous disparate data sources to enable the detection, quantification, contextualization, and reporting of methane emissions along the oil and gas supply chain. Such an integration would enable emissions reductions through early detection of super emitters, data-driven mitigation strategies, and improvedgreenhouse gas inventories. The GTI Energy (“GTI”)project team (“the team”) worked with a multitude of industry experts, stakeholders, and subject matter experts (SMEs) to collect guidance, insights, and information to inform the requirements and subsequent engineering, design, deployment, and operations of an integrated methane monitoring platform (IMMP). This final report describes the results of the team’s effort to execute the Integrated Methane Monitoring Platform Design project, ultimately providing an engineering, design, deployment, and operating plan (EDDOP) for the IMMP. This document provides additional information supporting the findings in the final report.

03 NATURAL GAS↗

DOE OSTI2023

Temperature Inhibition of Plasma-Driven Methane Conversion in DBD Systems

Low-temperature non-thermal plasmas produce highly reactive chemical environments made up of electrons, ions, radicals, and vibrationally excited molecules. These reactive species, when combined with catalysts, can help drive thermodynamically unfavorable chemical reactions at low temperatures and atmospheric pressure. The conversion of methane (CH 4 ) to produce other value-added chemicals is a good model system because of its applicability to a wide range of industries. To effectively create these plasma catalytic systems, a fundamental understanding of the plasma-phase chemistry alone is imperative. While there have been many studies on methane plasmas and how certain operating conditions (i.e., gas composition and power) affect the plasma, there is limited understanding on how changing bulk reaction temperature affects the plasma properties and ensuing plasma chemistry. Here, in this work, we use a dielectric barrier discharge to investigate the effects of temperature on the reaction chemistry and the plasma’s electrical properties in various methane-gas mixtures. Results show that increasing temperature leads to a reduction in methane conversion as well as changes to both the gas and dielectric material pre-breakdown, which manifests itself in temperature-dependent electrical properties of the plasma. Experiments at various temperatures and power show a positive correlation between key electrical plasma properties (average charge and lifetime per filament) and the measured methane conversion as a function of temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2016

Catalytic co-aromatization of ethanol and methane

This study demonstrates the technical feasibility of simultaneously converting ethanol and methane into liquid hydrocarbons at mild reaction conditions (400 °C and 1 atm) over silver and/or zinc modified zeolite catalysts. After GC-MS analysis, it is worth noting that aromatics are the major compounds contained in the liquid product collected from the run when 1%Ag/ZSM-5, particularly after H 2 pretreatment, is charged. Compared to the performance exhibited from the run with pure HZSM-5 support engaged, Ag addition into the HZSM-5 framework favors aromatics formation, which might be closely associated with better Ag dispersion and more abundance of strong surface acidic sites where aromatization might take place while Zn loading exerts a detrimental effect on the production of aromatics but promotes the ether generation possibly through dehydration reaction. Referred to that from its N 2 counterpart, the increased aromatics formation of the collected liquid product when methane is present indicates that methane existence might facilitate ethanol aromatization. Moreover, combined with the increased carbon number in the formed aromatics from CH 4 run when H 2 run is referred and zero liquid formation from CH 4 -alone test as well as more prominent endothermic feature of methane run and more importantly the notably increased 13 C signals in 13 C NMR spectra of the liquid product collected during ethanol conversion under 13 CH 4 environment, all the observations suggest that methane might be activated nonoxidatively and converted into higher hydrocarbons, preferentially into aromatics if suitable catalyst is charged under the assistance of co-existing oxygenated hydrocarbon. Lastly, the reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and cellulosic ethanol.

09 BIOMASS FUELS↗

DOE OSTI2018

A study of Ni/La-Al 2 O 3 catalysts: A competitive system for CO 2 methanation

Ni/La-γ-Al 2 O 3 samples containing 13.6 wt.% Ni and a variable amount of lanthana (0, 4, 14 and 37 wt.%) were prepared by incipient wetness impregnation, using silica-free γ-Al 2 O 3 support. The materials were characterized, as such or after reaction, with XRD, H 2 -TPR, IR, UV–vis-NIR, XPS and FE-SEM techniques. They were tested as catalysts for CO 2 methanation at atmospheric pressure at GHSV 55000 h –1 . The reaction is under kinetic control at T < 650–673 K, while the product mixture is under thermodynamic control above this temperature range. Lanthanum addition strongly increases the activity of Ni/γ-Al 2 O 3 for CO 2 methanation. Methane selectivity is increased to nearly 100% at low temperatures (T < 650 K). The CO 2 methanation reaction on La-doped Ni/γ-Al 2 O 3 occurs with similar activation energies (80 kJ/mol), and with slightly higher reaction order for hydrogen and lower reaction order for CO 2 than those observed for undoped Ni/γ-Al 2 O 3 . Lanthanum acts as a promoter because of the stronger basicity of the lanthana-alumina support allowing stronger adsorption of CO 2 as surface carbonates that can be act as “reactant reservoirs”. Finally, the Ni/La-alumina catalysts studied here are similarly effective as Ru/alumina catalysts for the selective CO 2 methanation at low temperature and atmospheric pressure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2019

The effect of CO on CO2 methanation over Ru/Al2O3 catalysts: a combined steady-state reactivity and transient DRIFT spectroscopy study

The reactivity of Ru/Al2O3 catalysts in the hydrogenation of CO/CO2 gas mixtures is investigated in this work. Accordingly kinetic measurements are carried out at process conditions of industrial interest (i.e., at high COx per-pass conversion and with concentrated COx/H2 streams), and the surface species on the catalyst are investigated through transient DRIFTS-MS analysis. The catalyst shows gradual deactivation when the methanation is carried out in the presence of CO in the gas feed at low temperatures (200-300 °C). However, stable performance is observed at higher temperatures, showing CH4 yields even higher than those observed during methanation of a pure CO2 feed. The catalyst deactivation at low temperature is reversible as thermal treatments at temperatures above 350 °C are able to restore the catalytic activity. DRIFTS-MS experiments revealed that CO2 methanation involves a reaction pathway where CO2 is adsorbed as bicarbonate on Al2O3 and successively hydrogenated to methane on Ru, passing through formate and carbonyl intermediates. In the presence of CO at low temperatures, the catalyst shows a higher CO coverage of the Ru sites, a larger formate coverage of alumina sites and the presence of adsorbed carbonaceous species, identified as hydrocarbon and carboxylate species. Carboxylates remain on the surface, effectively blocking adsorption sites thus leading to catalyst deactivation. However, working above the carboxylate decomposition temperature ensures a clean catalyst surface, resulting in stable and high performance in CO/CO2 methanation. Catalyst preparation, characterization and testing activity were carried out with a joint project between the Politecnico di Milano and the Italian National Agency for New Technologies, Energy and Sustainable Economic Development (ENEA), which is gratefully acknowledged. The authors gratefully acknowledge the financial support of the DRIFTS experiments by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. L.F. also acknowledges the Pacific Northwest National Laboratory (PNNL) for the financial support during his permanence as visiting student.

Methanation, Power-to-gas, Ru/Al2O3 catalyst, cata↗

DOE OSTI2022

A general strategy and a consolidated mechanism for low-methane hydrogenolysis of polyethylene over ruthenium

Polyethylene (PE) is one of the most environment-threatening plastic waste. Its Ru-catalyzed hydrogenolysis is rapid but produces too much methane. Here, in this study, low-density PE hydrogenolysis is performed at mild conditions and short times over Ru-doped zirconia catalysts (Ru-XZr, X = Ti, Nb, Ce, W, V, Mo, Fe) to determine low-methane catalysts. Methane is produced via direct terminal C-C scission and surface cascade of consecutive C-C scissions, with the latter sensitive to hydrogen availability and dominant in hydrogen-lean conditions. Reactivity studies, characterization and theory reveal that the most effective dopant oxides (W, V, and Mo) are intermediately reducible, as they store and supply extra hydrogen to Ru via reverse hydrogen spillover. This hydrogen readily hydrogenates and desorbs long alkyl surface intermediates that would otherwise produce cascade methane. Our proposed mechanism reconciles the low methane production achieved by increasing the hydrogen pressure or reducing the particle size and exposes the key selectivity descriptors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Intrinsic kinetics of water-inhibited ultra-lean methane oxidation over PtPd-Mg/ θ -Al 2 O 3 catalyst

Here, this study develops intrinsic methane oxidation kinetics for ultra-lean methane conditions in the presence of water over a highly active and stable PtPd–Mg/θ-Al 2 O 3 catalyst. Comprehensive laboratory experiments were conducted over a wide range of methane concentrations (150–1200 ppm CH 4 ), water contents (1–5% H 2 O), and industrially relevant space velocities (80,000 ≤ GHSV ≤ 160,000 h -1 ). These systematic experiments informed a two-dimensional, axisymmetric, multiscale reactor model that was used to develop and validate methane oxidation kinetics under practically relevant conditions, including non-isothermal operation and high conversion regimes. Combined experimental and modeling results revealed significant intraparticle diffusion resistance and transport-induced reaction exotherm at elevated temperatures, which limited catalyst utilization despite high intrinsic activity. These transport effects were explicitly incorporated into the reactor model, enabling accurate estimation of intrinsic kinetic parameters without reliance on conventional effectiveness-factor corrections. The resulting kinetic model successfully captured both kinetically controlled and mass-transfer-limited regimes and reliably predicted CH 4 conversion across broad ranges of temperature, methane concentration, and water content

Heat and mass transfer limitations↗

DOE OSTI2026

Life cycle analysis of hydrogen production via methane pyrolysis using plasma arc

Steam methane reforming of natural gas is the primary method of producing hydrogen in the United States, accounting for 95% of all hydrogen produced there. Methane pyrolysis, an alternative production pathway that decomposes natural gas into solid carbon and hydrogen, both eliminates CO 2 emissions associated with methane reforming and allows for additional income from carbon black. A life-cycle inventory of this process has been developed using ASPEN Plus to model the methane pyrolysis (plasma arc) process. From well to gate, hydrogen production via methane pyrolysis produces 2.78 kg CO 2 e/kg H 2 of greenhouse gas emissions using mass allocation of emissions between hydrogen and carbon black coproducts. The well-to-gate emissions are mainly driven by electricity consumption (∼38 kW h/kg H 2 ), which accounts for 81% of the emissions; if renewable electricity is used, well-to-gate emissions can be reduced to −0.448 kg CO 2 e/kg H 2 .

08 HYDROGEN↗

DOE OSTI2020

Selective activation of methane C–H bond in the presence of methanol

Direct methane to methanol (MTM) conversion over heterogeneous catalysts is a promising route for valorization of methane. The methane C-H bond activation is considered as the key step of the MTM and is the focus of considerable research activity. However, the formed methanol typically suffers from overoxidation largely due to the cleavage of a methanol C-H bond, whose bond dissociation energy is ca. 0.5 eV lower than that of the methane C-H bond, which usually translates to a transition state energy of the methanol C-H bond cleavage that is ca. 0.55 eV lower than that of methane whenever the reactions proceed through a radical mechanism. Furthermore, we propose a general approach for decreasing the transition state energy difference between the CH 4 and CH 3 OH C-H bond dissociation. When a metal-oxide supported cationic transition metal atom and a neighboring oxygen on the oxide surface serve as the active site, the transition state energy difference through a surface-stabilized pathway can be noticeably narrowed as compared with that of a radical pathway. For Ir, Pt and Rh-doped anatase TiO 2 (101), the CH 4 C-H bond activation can be preferred over that of CH 3 OH at significant methanol mole fraction. Also, for PdAu alloys containing adsorbed oxygen and positively charged Pd, calculations suggest in agreement with recent experiments (Science 367 (6474), 193-197) that the CH 4 C-H bond can be selectively activated in the presence of CH 3 OH.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Indicators of carbon alteration (ICAs) suggest patterns in reservoir methane emissions

Reservoir operations influence emissions via multiple causal pathways. In this paper, we quantify indicators of carbon alteration (ICAs) focused on methane. ICAs were chosen to reflect the potential for methane emission along four causal pathways: 1) water column mixing, 2) wet-dry cycles in sediment, 3) sediment redistribution, and 4) vegetation. We developed algorithms to calculate ICAs for three reservoirs along a longitudinal gradient in the Tennessee River basin of the southeast US. The ICAs revealed interesting longitudinal patterns. Indicators of both methane production and destruction increased downstream. The potential for ebullitive methane emissions driven by sub-daily water level fluctuations and emissions mediated by vegetation were higher in downstream mainstem reservoirs than in the upstream tributary reservoir. Along the remaining two pathways, longitudinal patterns were equivocal (sediment pathway) or suggested decreased emissions downstream (water-column mixing). We also observed seasonal patterns and, by combining ICAs, inferred times when ramping could be achieved with lower risk of emissions. The ICAs demonstrated here are the first step in quantifying mechanistic relationships between reservoir operation and methane emissions. In future, they may lead to improved operations in reservoir cascades and regional-scale estimates of emissions that account for differences among reservoirs.

Greenhouse gases↗

DOE OSTI2014

Towards eliminating systematic errors caused by the experimental conditions in Biochemical Methane Potential (BMP) tests

Highlights: • The evaluated factors introduce significant systematic errors (10–38%) in BMP tests. • Ambient temperature (T) has the most substantial impact (∼10%) at low altitude. • Ambient pressure (p) has the most substantial impact (∼68%) at high altitude. • Continuous monitoring of T and p is not necessary for kinetic calculations. - Abstract: The Biochemical Methane Potential (BMP) test is increasingly recognised as a tool for selecting and pricing biomass material for production of biogas. However, the results for the same substrate often differ between laboratories and much work to standardise such tests is still needed. In the current study, the effects from four environmental factors (i.e. ambient temperature and pressure, water vapour content and initial gas composition of the reactor headspace) on the degradation kinetics and the determined methane potential were evaluated with a 2{sup 4} full factorial design. Four substrates, with different biodegradation profiles, were investigated and the ambient temperature was found to be the most significant contributor to errors in the methane potential. Concerning the kinetics of the process, the environmental factors’ impact on the calculated rate constants was negligible. The impact of the environmental factors on the kinetic parameters and methane potential from performing a BMP test at different geographical locations around the world was simulated by adjusting the data according to the ambient temperature and pressure of some chosen model sites. The largest effect on the methane potential was registered from tests performed at high altitudes due to a low ambient pressure. The results from this study illustrate the importance of considering the environmental factors’ influence on volumetric gas measurement in BMP tests. This is essential to achieve trustworthy and standardised results that can be used by researchers and end users from all over the world.

09 BIOMASS FUELS↗

DOE OSTI2017

Anaerobic co-digestion of sugarcane press mud with vinasse on methane yield

Highlights: • Press mud and vinasse co-digestion was investigated. •Methane yield during co-digestion was 64% higher to mono-digestion. • Press mud and vinasse co-digestion increased process stability. - Abstract: The conversion efficiency of high solids waste digestion as sugarcane press mud (P) may be limited due to hydrolysis step. The option of co-digestion with vinasse, main liquid waste generated from ethanol production, was investigated under batch regime at mesophilic conditions (37.5 ± 1 °C) and the best mixture was evaluated under semicontinuous regime in stirred-tank reactors. The maximum values for methane yield in batch tests were for V{sub 75}/P{sub 25} and V{sub 50}/P{sub 50} mixtures (on basis of the chemical oxygen demand (COD) percentage added in the mixture), with an average value of 246 N mL CH{sub 4} g{sup −1} COD{sub fed}, which was 13% higher than that of press mud alone. A highest methane production rate of 69.6 N mL CH{sub 4} g{sup −1} COD{sub fed}{sup −1} d{sup −1} was obtained for the mixtureV{sub 75}/P{sub 25}. During the experiment carried out in CSTR reactors, the organic loading rate (OLR) was increased from 0.5 up to 2.2 g VS L{sup −1} d{sup −1}. Methane yields of 365 L CH{sub 4} kg{sup −1} VS and biogas productivities of 1.6 L L{sup −1} were obtained in co-digestion, which was 64% higher in comparison to mono-digestion. The performance of the process in mono-digestion was less stable than in co-digestion, with a significant fall of methane yield to 1.8 kg VS m{sup −3} d{sup −1}, and a partial inhibition of the methanogenic archaeas when the OLR was increased up to 2.2 kg VS m{sup −3} d{sup −1}. The co-digestion of vinasse with press mud is a good option for the treatment of streams at the alcohol-sugar industry.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2017

Phosphoketolase overexpression increases biomass and lipid yield from methane in an obligate methanotrophic biocatalyst

Microbial conversion of methane to high-value bio-based chemicals and materials offers a path to mitigate GHG emissions and valorize this abundant-yet -underutilized carbon source. In addition to fermentation optimization strategies, rational methanotrophic bacterial strain engineering offers a means to reach industrially relevant titers, carbon yields, and productivities of target products. The phosphoketolase pathway functions in heterofermentative bacteria where carbon flux through two sugar catabolic pathways to mixed acids (lactic acid and acetic acid) increases cellular ATP production. Importantly, this pathway also serves as an alternative route to produce acetyl-CoA that bypasses the CO 2 lost through pyruvate decarboxylation in the Embden-Meyerhof-Parnas pathway. Thus, the phosphoketolase pathway can be leveraged for carbon efficient biocatalysis to acetyl-CoA-derived intermediates and products. Here, we show that the industrially promising methane biocatalyst, Methylomicrobium buryatense , encodes two phosphoketolase isoforms that are expressed in methanol- and methane-grown cells. Overexpression of the PktB isoform led to a 2-fold increase in intracellular acetyl-CoA concentration, and a 2.6-fold yield enhancement from methane to microbial biomass and lipids compared to wild-type, increasing the potential for methanotroph lipid-based fuel production. Off-gas analysis and metabolite profiling indicated that global metabolic rearrangements, including significant increases in post-translational protein acetylation and gene expression of the tetrahydromethanopterin-linked pathway, along with decreases in several excreted products, coincided with the superior biomass and lipid yield observed in the engineered strain. Further, these data suggest that phosphoketolase may play a key regulatory role in methanotrophic bacterial metabolism. As a result, given that acetyl-CoA is a key intermediate in several biosynthetic pathways, phosphoketolase overexpression offers a viable strategy to enhance the economics of an array of biological methane conversion processes.

09 BIOMASS FUELS↗

DOE OSTI2025

Supported-Single Nickel Atom Catalysts for the Methanation of Carbon Dioxide

Synthesis of twenty-seven bimetallic catalysts consisting of nickel and one of nine different dopants (B, Co, Cu, Fe, Mg, Mn, Sn, V, and Zn) supported on three different metal oxides (Al 2 O 3 , CeO 2 , and SiO 2 ) is carried out via organometallic grafting. The catalysts are evaluated for their activity and selectivity for the CO 2 methanation reaction at a feed ratio of H 2 /CO 2 of 4 at 300 °C in a high-throughput flow reactor system. After in situ pre-activation (500 °C in H 2 ), Ni/Co/CeO 2 exhibited high conversion (84.3%) and selectivity for methane (99.6%). Ni/Co/CeO 2 was characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction, H 2 -temperature-programmed reduction (H 2 -TPR), and CO 2 -temperature-programmed desorption (CO 2 -TPD). HRTEM showed the presence of single Ni and Co atoms on ceria after pre-reduction at 500 °C and after the methanation reaction at 300 °C for 15 h. XPS determined that the strong interaction between Ni, Co, and ceria increased after the reduction, leading to a charge transfer between Ni and Ce that created oxygen vacancies in ceria. Nickel was found to be Ni 2+ in the as-prepared material and was partially reduced in the presence of cobalt and after the activation in H 2 at 500 °C. The DFT results show that both nickel and cerium exhibit lower Bader charges in the Ni/Co/CeO 2 system, confirming that the presence of cobalt enhances the reduction of both Ni and Ce through electronic interactions. This indicates that single cationic Ni atoms are highly effective for the methanation reaction. In conclusion, the organometallic grafting technique is found to be efficient for synthesizing catalysts with highly homogeneous dispersed species at low metal loadings (0.16 wt % Ni–0.15 wt % Co), which leads to high turnover frequency (up to 248.7 h –1 ) and durability for methanation.

CO2 conversion↗

DOE OSTI2020

A Pd III Sulfate Dimer Initiates Rapid Methane Monofunctionalization by H Atom Abstraction

An electrogenerated Pd III 2 species in fuming sulfuric acid is competent for rapid and concurrent methane monohydroxylation to methyl bisulfate (CH 3 OSO 3 H) and methane sulfonation to methanesulfonic acid (CH 3 SO 3 H). In situ NMR at 50 °C is used to track methane transformation exclusively to CH 3 OSO 3 H and CH 3 SO 3 H at high conversions. Integrating a set of kinetic and computational studies, the mechanism of methane monofunctionalization by Pd III 2 is examined. Here, experimental rate laws and common kinetic isotope effects for CH 3 OSO 3 H and CH 3 SO 3 H formation suggest that both transformations proceed via a common rate-limiting C-H activation step. Introduction of O 2 or Pd II,III 2 suppresses CH 3 SO 3 H generation, indicating a radical chain sequence. Although the metal-metal bonded Pd III 2 complex is a net two-electron oxidant, our aggregate kinetic data point to a mechanistic model that features rate-limiting H atom abstraction by the Pd III 2 complex to generate a methyl radical intermediate. The CH 3 • intermediate then recombines with Pd II,III 2 to furnish a CH 3 Pd III 2 intermediate that reductively eliminates CH 3 OSO 3 H. Alternatively, the CH 3 intermediate can enter a chain reaction with SO 3 to generate CH 3 SO 3 H. DFT computations support the radical-based C-H activation by Pd III 2 and delineate H atom abstraction pathways with computed reaction barriers and kinetic isotope effects (KIEs) that are consistent with experimental data. These mechanistic investigations challenge the paradigm of electrophilic C-H activation and highlight H atom abstraction as a potent pathway for selective methane C-H oxidative functionalization at high reaction rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗