Search Results (720)

In response to increasingly stringent emission regulations, low-carbon fuels have received significant attention as sustainable energy sources for internal combustion engines. This study investigates four representative low-carbon fuels, methane, methanol, hydrogen, and ammonia, by systematically summarizing their combustion characteristics and emission profiles, along with a review of existing after-treatment technologies tailored to each fuel type. For methane engines, unburned hydrocarbon (UHC) produced during low-temperature combustion exhibits poor oxidation reactivity, necessitating integration of oxidation strategies such as diesel oxidation catalyst (DOC), particulate oxidation catalyst (POC), ozone-assisted oxidation, and zoned catalyst coatings to improve purification efficiency. Methanol combustion under low-temperature conditions tends to produce formaldehyde and other UHCs. Due to the lack of dedicated after-treatment systems, pollutant control currently relies on general-purpose catalysts such as three-way catalyst (TWC), DOC, and POC. Although hydrogen combustion is carbon-free, its high combustion temperature often leads to elevated nitrogen oxide (NO_x) emissions, requiring a combination of optimized hydrogen supply strategies and selective catalytic reduction (SCR)-based denitrification systems. Similarly, while ammonia offers carbon-free combustion and benefits from easier storage and transportation, its practical application is hindered by several challenges, including low ignitability, high toxicity, and notable NO_x emissions compared to conventional fuels. Current exhaust treatment for ammonia-fueled engines primarily depends on SCR, selective catalytic reduction-coated diesel particulate filter (SDPF). Emerging NO_x purification technologies, such as integrated NO_x reduction via hydrogen or ammonia fuel utilization, still face challenges of stability and narrow effective temperatures. Full article

The catalytic decomposition of CH₄ is a promising method for producing high-purity CO_x-free hydrogen. A Ni-Al-LDH catalyst synthesized via coprecipitation was modified with alkali metals (Mg, La, Ca, or Li) through reconstruction to enhance catalytic activity and resistance to deactivation during catalytic methane decomposition (CMD). The catalysts were evaluated by two activation methods: H₂ reduction and direct heating with CH₄. The MgNA-R catalyst achieved the highest CH₄ conversion (65%) at 600 °C when reduced with H₂, attributed to a stronger Ni-Al interaction. Under CH₄ activation, LaNA-C achieved a 55% conversion at the same temperature, associated with a smaller crystallite size and higher reducibility due to La incorporation. Although all catalysts deactivated due to carbon deposition and/or sintering, LaNA-C was the only sample that could resist deactivation for a longer period, as La appears to have a protective effect on the active phase. Post-reaction characterizations revealed the formation of graphitic and filamentous carbon. Raman spectroscopy exhibited a higher degree of graphitization and structural order in LaNA-C, whereas SEM showed a more uniform distribution of carbon filaments. TEM confirmed the presence of multi-walled carbon nanotubes with encapsulated Ni particles in La-promoted samples. These results demonstrate that La addition improves the catalytic performance under CH₄ activation and carbon structure. This finding offers a practical advantage for CMD processes, as it reduces or eliminates the need to use hydrogen during catalyst activation. Full article

This study investigates the effects of samarium (Sm) promotion on the catalytic activity of 5 weight percent Ni catalysts for partial oxidation of methane (POM)-based hydrogen production supported on a Si-Al mixed oxide (10SiO₂+90Al₂O₃) system. Several 5% Ni-based catalysts supported on silica–alumina was used to test the POM at 600 °C. Sm additions ranged from 0 to 2 wt.%. Impregnation was used to create these catalysts, which were then calcined at 500 °C and examined using BET, H₂-TPR, XRD, FTIR, TEM, Raman spectroscopy, and TGA methods. Methane conversion (57.85%) and hydrogen yield (56.89%) were greatly increased with an ideal Sm loading of 1 wt.%, indicating increased catalytic activity and stability. According to catalytic tests, 1 wt.% Sm produced high CH₄ conversion and H₂ production, as well as enhanced stability and resistance to carbon deposition. Nitrogen physisorption demonstrated a progressive decrease in pore volume and surface area with the addition of Sm, while maintaining mesoporosity. At moderate Sm loadings, H₂-TPR and XRD analyses showed changes in crystallinity and increased NiO reducibility. Sm incorporation into the support and its impact on the ordering of carbon species were indicated by FTIR and Raman spectra. The optimal conditions to maximize H₂ yield were successfully identified through optimization of the best catalyst, and there was good agreement between the theoretical predictions (87.563%) and actual results (88.39%). This displays how successfully the optimization approach achieves the intended outcome. Overall, this study demonstrates that the performance and durability of Ni-based catalysts for generating syngas through POM are greatly enhanced by the addition of a moderate amount of Sm, particularly 1 wt.%. Full article

This review explores CO₂ methanation and steam methane reforming (SMR) as two key thermochemical processes governed by reversible reactions, each offering distinct contributions to carbon-neutral energy systems. The objective is to provide a comparative assessment of both processes, highlighting how reaction reversibility can be strategically leveraged for decarbonization. The study addresses methane production via CO₂ methanation and hydrogen production via SMR, focusing on their thermodynamic behaviors, catalytic systems, environmental impacts, and economic viability. CO₂ methanation, when powered by renewable hydrogen, can result in emissions ranging from −471 to 1076 kg CO₂-equivalent per MWh of methane produced, while hydrogen produced from SMR ranges from 90.9 to 750.75 kg CO₂-equivalent per MWh. Despite SMR’s lower production costs (USD 21–69/MWh), its environmental footprint is considerably higher. In contrast, methanation offers environmental benefits but remains economically uncompetitive (EUR 93.53–204.62/MWh). Both processes rely primarily on Ni-based catalysts, though recent developments in Ru-based and bimetallic systems have demonstrated improved performance. The review also examines operational challenges such as carbon deposition and catalyst deactivation. By framing these technologies through the shared lens of reversibility, this work outlines pathways toward integrated, efficient, and circular energy systems aligned with long-term sustainability and climate neutrality goals. Full article

Inspired by the active site of methane monooxygenase, we designed a Cu₂O cluster anchored in the six-membered nitrogen cavity of a C₂N monolayer (Cu₂O@C₂N) as a stable and efficient enzyme-like catalyst. Density functional theory (DFT) calculations reveal that the bridged Cu-O-Cu structure within C₂N exhibits strong electronic coupling, which is favorable for methanol formation. Two competing mechanisms—the concerted and radical-rebound pathways—were systematically investigated, with the former being energetically preferred due to lower energy barriers and more stable intermediate states. Furthermore, strain engineering was employed to tune the geometric and electronic structure of the Cu-O-Cu site. Biaxial strain modulates the Cu-O-Cu bond angle, adsorption properties, and d-band center alignment, thereby selectively enhancing the concerted pathway. A volcano-like trend was observed between the applied strain and the methanol formation barrier, with 1% tensile strain yielding the overall energy barrier to methanol formation (ΔG_overall) as low as 1.31 eV. N₂O effectively regenerated the active site and demonstrated strain-responsive kinetics. The electronic descriptor Δε (ε_d − ε_p) captured the structure–activity relationship, confirming the role of strain in regulating catalytic performance. This work highlights the synergy between geometric confinement and mechanical modulation, offering a rational design strategy for advanced C1 activation catalysts. Full article

The mixed oxides of Ni/ZrO₂, Ni-Ca/ZrO₂, Ni-Ba/ZrO₂, and Ni-Ba-Ca/ZrO₂ were prepared using the co-precipitation method at a pH of precisely 8.3. The catalytic mixed oxides of Ni/ZrO₂, Ni-Ca/ZrO₂, Ni-Ba/ZrO₂, and Ni-Ba-Ca/ZrO₂ were characterized using x-ray diffraction XRD, Brunauer Emmett Teller (BET), scanning electron microscopy (SEM), and metal dispersion for the screening of phase purity, surface area, and morphology. The mixed oxides are subjected to CO₂-TPD to quantify the basicity of every composition. The mixed oxide catalysts of Ni/ZrO₂, Ni-Ca/ZrO₂, Ni-Ba/ZrO₂, and Ni-Ba-Ca/ZrO₂ were screened for oxythermal reforming of CH₄ with CO₂ in a fixed bed tubular reactor at 800 °C. Among all catalysts, the Ba- and Ca- loaded Ni-Ba-Ca/ZrO₂ showed high conversion by the decomposition of methane and CO₂ disproportionation throughout the time on stream of 29 h. The high activity with stability led to less coke formation over Ni-Ba-Ca/ZrO₂ over the surface. The stable syngas production with an active catalyst bed contributed to the improved bimetallic synergy. The high surface basicity of Ni-Ba-Ca/ZrO₂ may keep actively gasifying the formed soot and allow for further stable reforming reactions. Full article

Non-catalytic partial oxidation (POX) of natural gas is gaining importance in low-carbon energy systems for methane conversion to acetylene, syngas, and olefins. However, uncontrolled polycyclic aromatic hydrocarbons (PAHs) and soot formation remain challenges. This work developed a Hierarchical-Integrated Mechanism (HI-Mechanism) by constructing detailed C₀-C₆, C₅-C₁₅ and C₁₆ mechanisms, and then hierarchically simplifying C₅-C₁₅ subsystems, ultimately integrating them into a final mechanism with 397 species and 5135 reactions. The HI-Mechanism accurately predicted shock tube ignition delays and major species concentrations. Microkinetic analyses, including production rates and reaction sensitivity, revealed key pathways and enabled reliable product distribution prediction. The HI-Mechanism provides theoretical guidance for optimizing POX of natural gas processes and can be extended to complex systems like heavy oil cracking, supporting clean energy technology development. Full article

This work deals with the catalytic steam reforming of raw syngas to increase the efficiency of coupling gasification with downstream processes (such as fuel cells and catalytic chemical syntheses) by producing high-temperature, ready-to-use syngas without cooling it for cleaning and conditioning. Such a combination is considered a key point for the future exploitation of syngas produced by steam gasification of biogenic solid fuel. The design and construction of an integrated gasification and gas conditioning system were proposed approximately 20 years ago; however, they still require further in-depth study for practical applications. A 3D model of the freeboard of a pilot-scale, fluidized bed gasification plant equipped with catalytic ceramic candles was used to investigate the optimal operating conditions for in situ syngas upgrading. The global kinetic parameters for methane and tar reforming reactions were determined experimentally. A fluidized bed gasification reactor (~5 kWth) equipped with a 45 cm long segment of a fully commercial filter candle in its freeboard was used for a series of tests at different temperatures. Using a computational fluid dynamics (CFD) description, the relevant parameters for apparent kinetic equations were obtained in the frame of a first-order reaction model to describe the steam reforming of key tar species. As a further step, a CFD model of the freeboard of a 100 kWth gasification plant, equipped with six catalytic ceramic candles, was developed in ANSYS FLUENT^®. The composition of the syngas input into the gasifier freeboard was obtained from experimental results based on the pilot-scale plant. Simulations showed tar catalytic conversions of 80% for toluene and 41% for naphthalene, still insufficient compared to the threshold limits required for operating solid oxide fuel cells (SOFCs). An overly low freeboard temperature level was identified as the bottleneck for enhancing gas catalytic conversions, so further simulations were performed by injecting an auxiliary stream of O₂/steam (50/50 wt.%) through a series of nozzles at different heights. The best simulation results were obtained when the O₂/steam stream was fed entirely at the bottom of the freeboard, achieving temperatures high enough to achieve a tar content below the safe operating conditions for SOFCs, with minimal loss of hydrogen content or LHV in the fuel gas. Full article

The production of synthetic natural gas in the context of power-to-gas is a promising technology for the utilization of CO₂. Ni-based catalysts supported on carbon nanotubes (CNTs) were prepared through incipient wetness impregnation and characterized using N₂ adsorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and temperature-programmed reduction (TPR). The catalysts were tested for CO₂ methanation in the 200–400 °C temperature range and at atmospheric pressure. The results demonstrated that the catalytic activity increased with the addition of the CNTs and Ni loading. The selectivity towards CH₄ was close to 100% for the Ni/ZrO₂/CNT catalysts. Reduction of the calcined catalyst at 500 °C using H₂ modified the surface chemistry of the catalyst, leading to an increase in the Ni particles. The CO₂ conversion was dependent on the Ni loading and the temperature reduction in the NiO species. The 10Ni/ZrO₂/CNT catalyst was highly stable in CO₂ methanation at 350 °C for 24 h. Thus, CNTs combined with Ni and ZrO₂ were considered promising for use as catalysts in CO₂ methanation at low temperatures. Full article

Ni-based catalysts have been widely used in catalytic reactions by researchers due to their advantages such as abundant resources, high catalytic activity and lower prices than precious metals. However, the problems of easy agglomeration and poor dispersion of Ni-based catalysts have hindered their large-scale application. Therefore, it is necessary to select a suitable preparation method to reduce the agglomeration of the catalyst and improve its dispersion. In this paper, the Ni-NiAl₂O₄/tourmaline composite material was prepared by using the microwave hydrothermal reduction method. The most favorable conditions for preparing NiAl₂O₄/tourmaline are as follows: using TEOA as the additive, the microwave hydrothermal temperature is 220 °C, the calcination temperature is 800 °C, and the addition amount of tourmaline is 7.4 wt.%. NiAl₂O₄ has a good dispersion over the surface of tourmaline support and the optimal NiAl₂O₄/tourmaline catalyst exhibits a specific surface area of 106.5 m²/g. Metallic nickel was reduced at 650 °C to further obtain Ni-NiAl₂O₄/tourmaline composites. Finally, the Ni-NiAl₂O₄/tourmaline composites showed significantly improved catalytic dry reforming of methane (DRM) activity compared to Ni-NiAl₂O₄ sample under low-temperature conditions (500–600 °C), meaning that the tourmaline carrier could effectively optimize the low-temperature catalytic performance of Ni-NiAl₂O₄. Full article

This study presents the results of an investigation of carbonate-containing sorbents for CO₂ capture with natural support materials—kaolin and calcium carbonate—at various loadings of the active phase of Na₂CO₃. The effects of the support type on the distribution of the active component, phase composition, and pore structure of the sorbents were studied. It was found that a Na₂CO₃ loading of 25 wt.% provides the best balance between sorption capacity and technological feasibility. The thermal stability and regeneration capacity of the sorbents were evaluated under high-temperature conditions, revealing high thermal stability of the Na₂CO₃/CaCO₃ system up to 1000 °C, along with its durability over multiple adsorption–desorption cycles. Kinetic studies on the Na₂CO₃/CaCO₃ sorbent using the shrinking core model demonstrated that the overall CO₂ chemisorption process is controlled by surface chemical reaction at temperatures below 50 °C. The obtained results demonstrate the high potential of CaCO₃-based sorbents for practical applications in low-temperature CO₂ capture technologies. A promising direction for the use of such sorbents within CCUS is the development of integrated systems, where CO₂ capture is combined with its conversion into valuable products (e.g., methane, methanol, formic acid) through catalytic processes. Full article

The use of CH₄ and CO₂ as fuels in direct internal reforming solid oxide fuel cells (DIR-SOFCs) is a promising strategy for efficient power generation with reduced greenhouse gas emissions. In this study, Ni catalysts supported on Ce–Pr mixed oxides with varying Pr contents (0–80 mol%) were synthesized, calcined at 1200 °C, and tested for dry reforming of methane (DRM), aiming at their application as catalytic layers in SOFC anodes. Physicochemical characterization (XRD, TPR, TEM) showed that increasing Pr loading enhances catalyst reducibility and promotes the formation of the Pr₂NiO₄ phase, which contributes to the generation of smaller Ni⁰ particles after reduction. Catalytic tests revealed that all samples exhibited low-carbon deposition, attributed to the large Ni crystallites. The catalyst with 80 mol% Pr showed the best performance, achieving the highest CH₄ conversion (72%), a H₂/CO molar ratio of 0.89, and improved stability. These findings suggest that Ni/Ce_0.2Pr_0.8 could be a promising candidate for use as a catalyst layer of anodes in DIR-SOFC anodes. Although electrochemical data are not yet available, future work will evaluate the catalyst’s performance and durability under SOFC-relevant conditions. Full article

The synthesis method of the Pr-doped CeO₂ catalyst support in Ni/Pr-CeO₂ CO₂ methanation catalysts is varied by changing the type/basicity of the precipitating solution and the hydrothermal treatment temperature. The use of highly basic NaOH as the precipitating agent and elevated hydrothermal treatment temperature (100 or 180 °C) leads to the formation of structured Pr-doped CeO₂ nanorods and nanocubes, respectively, whereas the use of a mildly basic NH₃-based buffer in the absence of hydrothermal treatment (i.e., co-precipitation) leads to an unstructured mesoporous morphology with medium-sized supported Ni nanoparticles. The latter catalyst (Ni/CP_NH3) displays a high surface area, high population of moderately strong basic sites, high oxygen vacancy population, and favorable Ni dispersion. These properties lead to a higher catalytic activity for CO₂ methanation (75% CO₂ conversion and 99% CH₄ selectivity at 350 °C) compared to the catalysts with structured nanorod and nanocube support morphologies, which are found to contain a significant amount of leftover Na from the synthesis procedure that can act as a catalyst inhibitor. In addition, the best-performing Ni/CP_NH3 catalyst is shown to be highly stable, with minimal deactivation during time-on-stream operation. Full article

Catalytic methane decomposition offers an attractive and sustainable pathway for producing CO_x-free hydrogen and valuable carbon nanotubes. This work investigates the innovative use of liquid metals, particularly gallium and indium, as promoters for iron catalysts based on a titanium dioxide and alumina composite to improve this process even more. In a fixed-bed reactor operating at 800 °C and atmospheric pressure, all catalyst activities for methane decomposition were thoroughly assessed while keeping the gas hourly space velocity at 6 L/g h. Surface area and porosity, H₂-temperature programmed reduction/oxidation, X-ray diffraction, Raman spectroscopy, scanning transmission electron microscopy, and thermogravimetry analysis were utilized to investigate the physicochemical properties of the catalyst. The result showed that iron supported on a titanium-alumina catalyst exhibited higher activity, stability, and reproducibility with a methane conversion of 90% and hydrogen production of 81% after three cycles, with 240 min for each cycle and stability for 480 min. In contrast, the liquid metal-promoted catalysts improved the metal-support interaction and textural properties, such as surface area, pore volume, and particle dispersion of the catalysts. Still, the catalytic efficiency significantly improved. However, the gallium-promoted catalyst displayed excellent reusability. The characterization of the spent catalyst proved that both the iron supported on a titanium-alumina and its gallium-promoted derivative produced graphitic carbon; on the contrary, the indium-promoted catalyst produced amorphous carbon. These results demonstrate how liquid metal promoters can be used to adjust the characteristics of catalysts, providing opportunities for improved reusability and regulated production of carbon byproducts during methane decomposition. Full article

Methane (CH₄) has attracted much attention regarding its use in electrochemical carbon dioxide reduction reaction (CO₂RR) due to its high mass-energy density; however, the uneven adsorption of intermediates on copper sites by conventional Cu-based catalysts limits the selective production of CH₄. The introduction of a second metal can effectively regulate the adsorption energy of intermediates on the Cu site. In this paper, a method of alloying Cu with oxyphilic metals (M) using rapid electrodeposition is presented; the synergistic effect of the bimetal effectively directed the reaction pathway toward CH₄. The best Faraday efficiency for methane occurred in the optimized Cu₃₀La₂₀ electrode, reaching 66.9% at −1.7 V vs. RHE potential. In situ infrared testing revealed that the *CHO intermediate—a critical species for the electrocatalytic conversion of CO₂ to CH₄—was detected on the Cu₃₀La₂₀ catalytic electrode. However, no *CHO intermediate was observed on the Cu₂₀La₃₀ electrode. Instead, the characteristic peak of the *OCCHO intermediate associated with C-C coupling emerged on the Cu₂₀La₃₀ catalyst. This indicates that the adsorbed oxygen-containing groups on lanthanum sites reacted with carbon-containing groups on copper sites to form C₂ products, serving as the primary reason for the shift in reduction products from methane to ethylene. Full article