Methane Activation Research Articles

Growth of diamond in liquid metal at 1 atm pressure.

Natural diamonds were (and are) formed (thousands of million years ago) in the upper mantle of Earth in metallic melts at temperatures of 900-1,400 °C and at pressures of 5-6 GPa (refs. 1,2). Diamond is thermodynamically stable under high-pressure and high-temperature conditions as per the phase diagram of carbon3. Scientists at General Electric invented and used a high-pressure and high-temperature apparatus in 1955 to synthesize diamonds by using molten iron sulfide at about 7 GPa and 1,600 °C (refs. 4-6). There is an existing model that diamond can be grown using liquid metals only at both high pressure and high temperature7. Here we describe the growth of diamond crystals and polycrystalline diamond films with no seed particles using liquid metal but at 1 atm pressure and at 1,025 °C, breaking this pattern. Diamond grew in the subsurface of liquid metal composed of gallium, iron, nickel and silicon, by catalytic activation of methane and diffusion of carbon atoms into and within the subsurface regions. We found that the supersaturation of carbon in the liquid metal subsurface leads to the nucleation and growth of diamonds, with Si playing an important part in stabilizing tetravalently bonded carbon clusters that play a part in nucleation. Growth of (metastable) diamond in liquid metal at moderate temperature and 1 atm pressure opens many possibilities for further basic science studies and for the scaling of this type of growth.

Insights into Fischer–Tropsch catalysis: current perspectives, mechanisms, and emerging trends in energy research

Fischer–Tropsch (FT) synthesis is an important module for the production of clean and sustainable fuels and chemicals, making it a topic of considerable interest in energy research. This mini-review covers the current literature on FT catalysis and offers insights into the primary products, the nuances of the FT reaction, and the product distribution, with particular attention to the Anderson–Schulz–Flory distribution (ASFD) and known deviations from this fundamental concept. Conventional FT catalysts, particularly Fe- and Co-based catalysis systems, are reviewed, highlighting their central role and the influence of water and water–gas shift (WGS) activity on their catalytic behavior. Various mechanisms of catalyst deactivation are also investigated, and the high methanation activity of Co-based catalysts is illustrated. To make this complex field accessible to a broader audience, we explain conjectured reaction mechanisms, namely, the carbide mechanism and CO insertion. We discuss the complex formation of a wide range of products, including olefins, kerosenes, branched hydrocarbons, and by-products such as alcohols and oxygenates. The article goes beyond the traditional scope of FT catalysis by addressing topics of current interest, including the direct hydrogenation of CO2 for power-to-X applications and the use of bifunctional catalysts to produce tailored FT products, most notably for the production of sustainable aviation fuel (SAF). This mini-review provides a holistic overview of the evolving landscape of FT catalysts and is aimed at both experienced researchers and those new to the field while covering current and emerging trends in this important area of energy research.

Direct conversion of methane to aromatics and hydrogen via a heterogeneous trimetallic synergistic catalyst

Non-oxidative methane dehydro-aromatization reaction can co-produce hydrogen and benzene effectively on a molybdenum-zeolite based thermochemical catalyst, which is a very promising approach for natural-gas upgrading. However, the low methane conversion and aromatics selectivity and weak durability restrain the realistic application for industry. Here, a mechanism for enhancing catalysis activity on methane activation and carbon-carbon bond coupling has been found to promote conversion and selectivity simultaneously by adding platinum–bismuth alloy cluster to form a trimetallic catalyst on zeolite (Pt-Bi/Mo/ZSM-5). This bimetallic alloy cluster has synergistic interaction with molybdenum: the formed CH3* from Mo2C on the external surface of zeolite can efficiently move on for C-C coupling on the surface of Pt-Bi particle to produce C2 compounds, which are the key intermediates of oligomerization. This pathway is parallel with the catalysis on Mo inside the cage. This catalyst demonstrated 18.7% methane conversion and 69.4% benzene selectivity at 710 °C. With 95% methane/5% nitrogen feedstock, it exhibited robust stability with slow deactivation rate of 9.3% after 2 h and instant recovery of 98.6% activity after regeneration in hydrogen. The enhanced catalytic activity is strongly associated with synergistic interaction with Mo and ligand effects of alloys by extensive mechanism studies and DFT calculation.

Enhanced CO2 methanation activity of Ni-Rutile-based catalyst by tuning the metal−support interaction with Fe doping

CO2 methanation is an effective way for CO2 recycling, and nickel-based catalysts have attracted much attention in this field due to their excellent CH4 selectivity and cost-effectiveness; however, their applications are limited by their suboptimal catalytic activity. In this work, the catalytic activity of Ni-rutile-based catalysts was increased by almost an order of magnitude simply by doping the rutile with Fe. Series characterizations show that three factors that mainly contributed to the improved catalytic performance of the Ni/Fe-Rutile, which are the reduction of the Ni size, the increase of the basic sites, and the inhibition of the encapsulation of the Ni particles by the support. With Fe doping, the OH and oxygen vacancies on the rutile surface were reduced, which made the support difficult to reduce and thus suppressed the encapsulation of Ni by the support. As a result, the number of exposed active sites on the Ni/Fe-Rutile which with a smaller Ni size was further successfully increased, and the catalytic activity was significantly improved. This study provides new ideas for the design of activity-enhanced supported catalysts from the perspective of tuning the metal-support interaction and may be applicable to other reducible oxide-supported metal catalysts.

Anionic oxyl radical formed on CrVI-oxo anchored on the defect site of the UiO-66 node facilitates methane to methanol conversion.

The direct conversion of methane to methanol has attracted increasing interest due to abundant and low-cost natural gas resources. Herein, by anchoring Cr-oxo/-oxyhydroxides on UiO-66 metal-organic frameworks, we demonstrate that reactive anionic oxyl radicals can be formed by controlling the coordination environment based on the results of density functional theory calculations. The anionic oxyl radicals produced at the completely oxidized CrVI site acted as the active species for facile methane activation. The thermodynamically stable CrVI-oxo/-oxyhydroxides with the anionic oxyl radicals catalyze the activation of the methane C-H bond through a homolytic mechanism. An analysis of the results showed that the catalytic performance of the active oxyl species correlates with the reaction energy of methane activation and H adsorption energies. Following methanol formation, N2O can regenerate the active sites on the most stable CrVI oxyhydroxides, i.e., the Cr(O)4Hf species. The present study demonstrated that the anionic oxyl radicals formed on the anchored CrVI oxyhydroxides by tuning the coordination environment enabled facile methane activation and facilitated methanol production.

Assembling bifunctional ceria-zirconia electrocatalyst for efficient electrochemical conversion of methane at room temperature

The electrochemical conversion of methane to C2 compounds at room temperature is reported using CeO2-ZrO2 electrocatalysts. The mixed oxide electrocatalysts produced methanol, ethanol, and acetone, along with traces of acetaldehyde and isopropanol, under a polarization of 1.2 V with ∼ 50 % Faradaic efficiency. Detailed characterization of the CeO2-ZrO2 revealed the formation of nanoparticles (7–9 nm mean size) composed of ceria-zirconia solid solution or a mixture of ceria with both tetragonal and monoclinic zirconia polymorphs depending on the assembling configuration of the electrocatalyst. Samples with separated phases and limited solid solution formation showed the highest electrochemical activity, indicating that an optimal assembly of ceria and zirconia was crucial to achieving efficient conversion with high Faradaic efficiency and selectivity. Such high electrochemical activity observed for the phase separated CeO2-ZrO2 electrocatalyst suggests that a synergic effect between ceria and zirconia is required for the critical reaction steps, such as the activation and partial oxidation of methane. The experimental results point to credible routes to efficiently convert methane into valuable chemicals in mild conditions.

Contact-Electro-Catalysis for Direct Oxidation of Methane under Ambient Conditions.

The conversion of methane under ambient conditions has attracted significant attention. Although advancements have been made using active oxygen species from photo- and electro- chemical processes, challenges such as complex catalyst design, costly oxidants, and unwanted byproducts remain. This study exploits the concept of contact-electro-catalysis, initiating chemical reactions through charge exchange at a solid-liquid interface, to report a novel process for directly converting methane under ambient conditions. Utilizing the electrification of commercially available Fluorinated Ethylene Propylene (FEP) with water under ultrasound, we demonstrate how this interaction promote the activation of methane and oxygen molecules. Our results show that the yield of HCHO and CH3OH can reach 467.5 and 151.2 μmol ⋅ gcat -1, respectively. We utilized electron paramagnetic resonance (EPR) to confirm the evolution of hydroxyl radicals (⋅OH) and superoxide radicals (⋅OOH). Isotope mass spectrometry (MS) was employed to analyze the elemental origin of CH3OH, which can be further oxidized to HCHO. Additionally, we conducted density functional theory (DFT) simulations to assess the reaction energies of FEP with H2O, O2, and CH4 under these conditions. The implications of this methodology, with its potential applicability to a wider array of gas-phase catalytic reactions, underscore a significant advance in catalysis.

Contact‐Electro‐Catalysis for Direct Oxidation of Methane under Ambient Conditions

AbstractThe conversion of methane under ambient conditions has attracted significant attention. Although advancements have been made using active oxygen species from photo‐ and electro‐ chemical processes, challenges such as complex catalyst design, costly oxidants, and unwanted byproducts remain. This study exploits the concept of contact‐electro‐catalysis, initiating chemical reactions through charge exchange at a solid–liquid interface, to report a novel process for directly converting methane under ambient conditions. Utilizing the electrification of commercially available Fluorinated Ethylene Propylene (FEP) with water under ultrasound, we demonstrate how this interaction promote the activation of methane and oxygen molecules. Our results show that the yield of HCHO and CH3OH can reach 467.5 and 151.2 μmol ⋅ gcat−1, respectively. We utilized electron paramagnetic resonance (EPR) to confirm the evolution of hydroxyl radicals (⋅OH) and superoxide radicals (⋅OOH). Isotope mass spectrometry (MS) was employed to analyze the elemental origin of CH3OH, which can be further oxidized to HCHO. Additionally, we conducted density functional theory (DFT) simulations to assess the reaction energies of FEP with H2O, O2, and CH4 under these conditions. The implications of this methodology, with its potential applicability to a wider array of gas‐phase catalytic reactions, underscore a significant advance in catalysis.

Plasma‐catalytic CO2 methanation over NiO/bentonite catalysts prepared by solution combustion synthesis

AbstractA solution combustion synthesis (SCS) process to prepare nickel catalyst over bentonite (NiO/Ben) is reported. Compared to the traditional impregnation method, NiO/ben produced by SCS has smaller nickel particle size and higher dispersion. With a metal loading of 20 wt%, the afforded NiO/Ben demonstrates excellent catalytic activity for CO2 methanation in a dielectric barrier discharge reactor. In certain discharge conditions (H2:CO2 ratio of 5 in feed gas, discharge input power of 45 W, and gas hourly space velocity of 11 320 h−1), CO2 conversion and CH4 selectivity are as high as 55.8% and 84.6%, respectively. Under the conditions of plasma configuration, the strong interaction between the nickel species and the support plays an important role in the CO2 methanation process.

Enhanced co-production of high-quality syngas and highly-concentrated hydrogen via chemical looping steam methane reforming over Ni-substituted La0.6Ce0.4MnO3 oxygen carriers

Chemical looping steam methane reforming (CLSMR) is increasingly attracting more and more attention as a promising technology for co-production of syngas and hydrogen. However, low reactivity, poor selectivity and weak resistance to carbon deposition of oxygen carriers (OCs) probably discourage further commercial application of CLSMR. With this background, a novel strategy of incorporating Ce and Ni into LaMnO3 is advised to promote lattice oxygen migration rate and improve syngas selectivity. The redox activity and cycle stability of La0.6Ce0.4Mn1−xNixO3 for CLSMR are explored in a fixed-bed reactor coupling with various characterization methods. The characterization results show that La0.6Ce0.4Mn1−xNixO3 OCs still maintain the standard perovskite structures and well-ordered skeleton. The introduction of Ce3+ induces large amounts of oxygen vacancies on the surface of OCs and improve the syngas selectivity of methane reforming, leading to higher oxygen mobility and lower carbon deposition. Meanwhile, the experimental results also confirm that the doping of Ni into La0.6Ce0.4MnO3 can greatly improve the oxygen-donation ability and effectively provide more active sites for reaction with methane. While excessive Ni in perovskite will enhance the methane dissociation, which is the main reason of carbon deposits. The proper amount of Ni doping can well match the methane activation rate to migration rate of bulk lattice oxygen that is feasible to realize the balance between productivity and efficiency. In addition, the reduced metal elements along with great amounts of oxygen vacancies together contribute to more active sites for the following steam splitting which avails to produce high-purity H2. La0.6Ce0.4Mn0.7Ni0.3O3 oxygen carrier eventually achieve syngas yield of 2.8 mmol/g H2 and 1.4 mmol/g CO that is closed to the ideal value without obvious carbon deposition, and pure H2 yield of 3.8 mmol/g, exhibiting the best redox performance and good regenerability. Meanwhile, La0.6Ce0.4Mn0.7Ni0.3O3 can still maintain high redox activity and basic perovskite structure after 15 cyclic redox tests, illustrating a desirable stability and reliability. In summary, this study offers a valuable and effective strategy to tackle with the bottleneck of CLSMR, paving the way of doping transition metal as a pathway of modulating reaction performance and stability of OCs in chemical looping processes.

Construction of multi-porous Ni-based monolithic catalyst by combining wood carbon and SBA-15 for strengthening CO2 methanation

Monolithic catalysts meet the needs of practical application compared with powder catalysts. In this work, we constructed a Ni-based monolithic catalyst (Ni/SAB-15/WWC) by in situ growth of rod-like mesoporous SBA-15 in the microchannels of wood carbon. The small Ni-based nanoparticles (∼5.3 nm) were uniformly dispersed into the mesoporous channels via a post-loading method. The monolithic Ni/SAB-15/WWC catalyst with a multilevel porous structure could provide a laminar gas flow on the surface of Ni active sites, increasing the low-temperature activity and high-temperature durability of CO2 methanation. The Ni/SAB-15/WWC with low Ni loading (∼2%) displayed superior CO2 methanation catalytic performance in terms of low-temperature activity and CH4 selectivity compared with the powder Ni/SAB-15 with high Ni loading (∼15 %). The combination of wood carbon and mesoporous materials is an innovative strategy for the design monolithic catalysts with low metal loading and excellent catalytic performance.

Hydrogen production by biogas reforming using Ni/MgO-Al2O3 catalysts

Hydrogen has been pointed out as a highly potential energy source for the future due to its flexibility in production and utilization. In order to obtain hydrogen sustainably, technologies that use renewable raw materials must be developed. In this context, this work proposes hydrogen production from biogas reforming. Ni/MgO-Al2O3 catalysts, containing 20 wt% of NiO and 10 wt% of MgO, were prepared by three methodologies (wet impregnation, coprecipitation, and citrate) and compared with Ni/Al2O3. The catalyst prepared by impregnation exhibited the highest Ni dispersion and basicity, with the highest activity in methane reforming with CO2 (CO2/CH4 = 1) at temperatures between 600 and 800 °C. This catalyst presented high stability during 100 h of reaction at 700 °C (92 % of CH4 conversion and 95 % of CO2 conversion), with a lower coking rate than Ni/Al2O3. Coke was predominantly graphitic for all catalysts, but the catalyst prepared by coprecipitation showed a higher proportion of amorphous coke and the lowest coking rate.

CO-Assisted Methane Oxidation into Oxygenates over Surface Platinum-Titanium Alloyed Layers.

Methane oxidation using molecular oxygen remains a grand challenge in which the obstacle is not only the activation of methane but also the reaction with oxygen, considering the mismatch of the ground spin states. Herein, we report TiO2-supported Pt nanocrystals (Pt/TiO2) with surface Pt-Ti alloyed layers that directly convert methane into oxygenates by using O2 as the oxidant with the assistance of CO. The oxygenate yield reached 749.8 mmol gPt-1 in a H2O aqueous solution over 0.1% Pt/TiO2 under 31 bar of mixed gas (20:5:6 CH4:CO:O2) at 150 °C for 3 h, while the CH3OH selectivity was 62.3%. On the basis of the control experiments and spectroscopic results, we identified the surface Pt-Ti alloy as the active sites. Moreover, CO promoted the dissociation of O2 on the surface of Pt-Ti alloyed layers and the subsequent activation of CH4 to form oxygenated products.

Methane-H2S Reforming Catalyzed by Carbon and Metal Sulfide Stabilized Sulfur Dimers.

H2S reforming of methane (HRM) provides a potential strategy to directly utilize sour natural gas for the production of COx-free H2 and sulfur chemicals. Several carbon allotropes were found to be active and selective for HRM, while the additional presence of transition metals led to further rate enhancements and outstanding stability (e.g., Ru supported on carbon black). Most metals are transformed to sulfides, but the carbon supports prevent sintering under the harsh reaction conditions. Supported by theoretical calculations, kinetic and isotopic investigations with representative catalysts showed that H2S decomposition and the recombination of surface H atoms are quasi-equilibrated, while the first C-H bond scission is the kinetically relevant step. Theory and experiments jointly establish that dynamically formed surface sulfur dimers are responsible for methane activation and catalytic turnovers on sulfide and carbon surfaces that are otherwise inert without reaction-derived active sites.

Enhanced CO2 methanation activity over Ni/CeO2 catalyst by adjusting metal-support interactions

CO2 methanation is an essential means of utilizing CO2, which is crucial to solving environmental problems and alleviating energy crisis. The design and development of high- performance low temperature CO2 methanation catalysts is the key to its further application. In this work, the metal-support interaction of Ni/CeO2 catalyst was regulated by changing the calcination temperature and Ni loadings to optimize the CO2 methanation performance. The results showed that 5NiCe-800 exhibited the best CO2 conversion of 83.1 % and 98.0 % CH4 selectivity at 350 °C, since it has a suitable Ni-CeO2 interaction, higher oxygen vacancy concentration, great reducibility and better basic site distribution. The reaction mechanism and the synergistic effect of CeO2 and Ni in CO2 methanation was revealed by in-situ FTIR, which is of great significance for the development of efficient CeO2 supported Ni-based for CO2 methanation.

Impact of varied zeolite materials on nickel catalysts in CO2 methanation

Ni catalysts supported on 4A, 5A, 13X, ZSM-5, and BEA zeolites were prepared using the vacuum-heating method for CO2 methanation. These support materials play a pivotal role in shaping the catalysts' properties and their catalytic performance. High-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray spectroscopy (EDS) mappings suggest a significant concentration of Ni nanoparticles situated on the external surfaces of catalysts with low Si/Al ratios zeolites (Ni-4A, Ni-5A, and Ni-13X). These Ni nanoparticles exhibit characteristics of weaker metal-support interaction, lower metal reduction temperatures, and moderate H2 adsorption activity. Moreover, these low Si/Al ratio zeolites demonstrate robust CO2 adsorption activity. These properties endow Ni-5A and Ni-13X catalysts with heightened CO2 conversion (70.4–70.9%) and methane selectivity (92.4–96.4%). In contrast, high Si/Al ratio zeolite-based catalysts (Ni-ZSM-5 and Ni-BEA) exhibit smaller Ni particles, strong metal-support interaction and weaker CO2 adsorption activity, resulting in reduced CO2 methanation activity and decreased methane selectivity (71.2–73.4%). The normalized CO2 conversion rate presents a correlation with the average Ni particle size.

Spectroscopic Characterization of Thermal Methane Activation by Lewis-Acid-Base Pair in a Gas-Phase Metal Nitride Anion Ta2N3.

Activation and transformation of methane is one of the "holy grails" in catalysis. Understanding the nature of active sites and mechanistic details via spectroscopic characterization of the reactive sites and key intermediates is of great challenge but crucial for the development of novel strategies for methane transformation. Herein, by employing photoelectron velocity-map imaging (PEVMI) spectroscopy in conjunction with quantum chemistry calculations, the Lewis acid-base pair (LABP) of [Taδ+-Nδ-] unit in Ta2N3 - acting as an active center to accomplish the heterolytic cleavage of C-H bond in CH4 has been confirmed by direct characterization of the reactant ion Ta2N3 - and the CH4-adduct intermediate Ta2N3CH4 -. Two active vibrational modes for the reactant (Ta2N3 -) and four active vibrational modes for the intermediate (Ta2N3CH4 -) were observed from the vibrationally resolved PEVMI spectra, which unequivocally determined the structure of Ta2N3 - and Ta2N3CH4 -. Upon heating, the LABP intermediate (Ta2N3CH4 -) containing the NH and Ta-CH3 unit can undergo the processes of C-N coupling and dehydrogenation to form the product with an adsorbed HCN molecule.

Acid treatment enhances the methane combustion activity of LaFeO3 perovskite catalyst

The catalytic combustion of methane has gained much attention as a sustainable technology, due to concerns about the environmental impact of unburnt methane emissions from the natural gas vehicles. Researchers have explored alternatives to precious metal catalysts for methane combustion, with a focus on perovskite oxides known for their excellent activity and sintering-resistance capacity. In this study, LaFeO3 perovskite material was synthesized and subsequently subjected to a nitric acid etching treatment to modify its surface. It was found that the acid preferentially dissolved La cations from LaFeO3 surface while the perovskite phase was unchanged, as a consequence, the etched LaFeO3 shows improvement in methane combustion activity. The best performance was achieved in the sample with one-hour surface etched treatment, which suggests that the appropriate surface reconstruction induced by acid treatment promotes the formation of more active Fe sites on the surface and reduces the energic barriers of methane activation. This work presents a straightforward and effective approach to tailor the exposed surface properties of perovskites, thereby enhancing their activity in hydrocarbon combustion reactions.

Photocatalytic methane conversion to high-value chemicals

Methane has a substantial and widespread reserve on Earth. As a very abundant carbon and hydrogen source, as well as an energy vector, upgrading methane to higher-value fuels and chemicals (carbon oxygenates, C₂₊ hydrocarbons, et al.) is a promising technology in the supply of energy and chemicals by a low-carbon process. Due to the stable and inert nature of methane, activating and converting the molecule is extremely challenging. Currently, commercial methane conversion technology operates at high temperatures and/or high pressure, suffering from intense energy consumption and high capital investment. Photocatalysis, using photons as the only energy input, can operate at mild temperatures and under atmospheric pressure, which is a promising and green technology for methane conversion to highvalue products. In this review, fundamental understandings of photocatalytic methane activation and product yield involving different oxidants are discussed. Then recent advances in photocatalysts for methane conversion to hydrocarbons and oxygenates are detailed, including the relevant reaction mechanism and reaction pathways. Finally, the challenges and perspectives for photocatalytic methane conversion will be discussed based on the current progress and fundamental understanding.

Structural design and particle size examination on NiO-CeO2 catalysts supported on 3D-printed carbon monoliths for CO2 methanation

3D-printed high-surface carbon monoliths have been fabricated and tested as catalyst supports of CO2 methanation active phases (NiO-CeO2, 12 wt% Ni). The carbon carriers show a developed microporosity and good adherence to the catalytic phases of NiO-CeO2, showing great stability and cyclability. Two monolith designs were used: a conventional parallel-channeled structure (honeycomb) and a complex 3D network of non-linear channels built upon interconnected circular sections (circles), where flow turbulences along the reactant gas path are spurred. The effect of the active phases particle size on the catalyst distribution and the overall performance has been assessed by comparing NiO-CeO2 nanoparticles of 7 nm average (Np), with a reference counterpart of uncontrolled structure (Ref). The improved radial gases diffusion in the circles monolith design is confirmed, and nanoparticles show enhanced CO2 methanation activity than the uncontrolled-size active phase at low temperatures (< 300 ºC). On the contrary, the Ref catalysts achieve higher CH4 production at higher temperatures, where the reaction kinetics is controlled by mass transfer limitations (T > 300 ºC). SEM and Hg porosimetry evidence that nanoparticles are deposited at deeper penetration through the narrow micropores of the carbon matrix of the monolithic supports, which tend to accumulate on the channels surface remaining more accessible to the reactant molecules. Altogether, this study examines the impact of the channel tortuosity and the active phase sizing on the CO2 methanation activity, serving as ground knowledge for the further rational and scalable fabrication of carbon monolith for catalytic applications.