Search Results (54)

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

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

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

In this study, the authors employed first-principles calculations to investigate the adsorption and decomposition processes involved in non-catalytic growth of vapor-growth carbon fiber (VGCF) using a non-catalytic growth method. The adsorption and decomposition mechanisms of methane and its decomposition products on the substrate were investigated with the adsorption energy, transition state analysis, and projected density of states (PDOS). The results indicated that the surface adsorption difficulty for CH₄ and its decomposition products followed the following order: H > CH₄ ≈ CH₃ > CH₂ > CH > C. The adsorption energy analysis indicates that the adsorption of CH₄, CH₃, and H is classified as physical adsorption, whereas the adsorption of CH₂, CH, and C is classified as chemical adsorption. Adsorption of all particles is exothermic and adsorption can occur. The transition state calculations indicate that the decomposition of CH₄ is the rate-determining step in the decomposition reaction. PDOS analysis not only verified the results of adsorption energy analysis but also investigated the effect of adsorption particles. This work is helpful for advancing the application of non-catalytic growth processes to the synthesis of VGCF and enhancing the understanding of the mechanisms governing non-catalytic VGCF formation. Full article

The continuous growth in world energy demands along with the urgent need for decarbonization are strong motivations for the development and usage of sustainable fuels. Hydrogen is highly anticipated to replace fossil fuels in energy production, as it is one of the cleanest energy sources with high energy density per weight. Among the hydrogen production methods, catalytic methane pyrolysis (CMP) stands out as it can contribute to the decarbonization process, since the only co-products include valuable carbon structures and no greenhouse emissions. Cobalt has been shown to be a competent metallic catalytic material with high activity in relation to hydrogen production and selectivity towards valuable carbon nanotubes (CNTs), or carbon nanofibers (CNFs). This review article aims to offer insights relevant to future developments in CMP, by reporting the advantages of methane decomposition over cobalt catalysts. It provides a summary of the factors that influence both hydrogen yield and carbon growth. More specifically, the impacts of different metal loadings and the benefits of utilizing both support carriers and bimetallic systems are addressed. Last but not least, the findings on the most efficient preparation procedures and the optimum operating conditions are also revealed, as supported by published experimental data. Full article

To reach agreed-on climate goals, it is necessary to develop new energy carriers and industrial materials that are carbon-neutral. To combat global warming and keep Earth’s temperature from increasing by 1.5 °C, some of these solutions need to be carbon-negative. This study fulfills this criterion by producing clean hydrogen and biocarbon suitable for the metallurgic industry through the thermal decomposition of methane using biocarbon as a catalyst. Five different biomass samples were used to prepare biocarbons at a pyrolysis temperature of 1000 °C with a holding time of 90 min. When methane was cracked at 1100 °C with a holding time of 90 min, the highest hydrogen production was 105 mol/kg biocarbon, achieved using birch bark. The lowest hydrogen yield, of 68 mol/kg biocarbon, was achieved with steam-explosion pellets. All the biocarbons showed substantial carbon deposition from cracked methane on their surfaces, with the highest deposition on birch bark and spruce wood biocarbons of 42% relative to the biocarbon start weight. The carbon deposition increased with the decomposition temperature, the methane share in the purge gas and the holding time. The steam-explosion pellets, after deactivation, had a CO₂ reactivity that was comparable to coke, a reducing agent that is commonly used in manganese-producing industries. About 90% of the potassium and sodium were removed from the biocarbon during catalytic decomposition of methane performed at 1100 °C. The alkali removal was calculated relative to the biocarbon produced under the same conditions, but with 100% N₂ purge instead of CH₄. After catalytic decomposition, the surface area of the biocarbon was reduced by 11–34%, depending on the biocarbon type. Full article

COx-free H₂, along with uniform carbon nanotubes, can be achieved together in high yield by CH₄ decomposition. It only needs a proper catalyst and reaction condition. Herein, Fe-based catalyst dispersed over titania-incorporated-alumina (Fe/Ti-Al), with the promotional addition of lanthanides, like CeO₂ and La₂O₃, over it, is investigated for a methane decomposition reaction at 800 °C with GHSV 6 L/(g·h) in a fixed-bed reactor. The catalysts are characterized by temperature-programmed reduction (TPR), powder X-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). The promoted catalysts are facilitated with higher surface area and enhanced dispersion and concentration of active sites, resulting in higher H₂ and carbon yields than unpromoted catalysts. Ceria-promoted 20Fe/Ti-Al catalyst had the highest concentration of active sites and always attained the highest activity in the initial hours. The 20Fe-2.5Ce/Ti-Al catalyst attains >90% CH₄ conversion, >80% H₂-yield, and 92% carbon yield up to 480 min time on stream. The carbon nanotube over this catalyst is highly uniform, consistent, and has the highest degree of crystallinity. The supremacy of ceria-promoted catalyst attained >90% CH₄ conversion even after the second cycle of regeneration studies (against 87% in lanthanum-promoted catalyst), up to 240 min time on stream. This study plots the path of achieving catalytic and carbon excellence over Fe-based catalysts through CH₄ decomposition. Full article

In a previous study, we developed an integrated reaction system combining NH₃ decomposition and CO₂ methanation within a membrane reactor, significantly enhancing reactor performance through efficient H₂ separation. Ru/Ba/γ-Al₂O₃ and Ru/ZrO₂ were employed as catalysts for each reaction. To ensure the accuracy and reliability of our results, they were validated through 1D models using FlexPDE Professional Version 7.21/W64 software. Key parameters such as reactor arrangement, catalyst bed positioning, overall heat transfer coefficient, rate constants, and H₂ permeance were investigated to optimize system efficiency. The study revealed that positioning the NH₃ decomposition on the shell side and CO₂ methanation on the tube side resulted in a better performance. Additionally, shifting the methanation catalyst bed downward by approximately one-eighth (10 mm from 80 mm) achieves the highest CO₂ conversion. A sensitivity analysis identified the rate constant of the NH₃ decomposition catalyst and the H₂ permeance of the membrane as the most influential factors in enhancing CO₂ conversion. This highlights the priority of improving membrane H₂ permeance and catalytic activity for NH₃ decomposition to maximize system efficiency. Full article

Catalytic methane decomposition (CMD) reaction is considered a promising process for converting greenhouse gas CH₄ into hydrogen and high-value-added carbon materials. In this work, a series of Al₂O₃-supported FeCo alloy catalysts were successfully prepared in the CMD process. Compared to the pre-reduced catalysts, the in situ reduced FeCo alloy catalysts showed higher methane conversion rates, with the highest reaching 83% at 700 °C, due to the finer active nanoparticle size and greater exposure of active site. Furthermore, the time-on-stream tests demonstrated that the catalytic activity of in situ reduced FeCo alloy catalysts could remain above 92.3% of the highest catalytic activity after 10 h. In addition, TEM analyses of the carbon products from the CMD in situ reduced catalysts revealed the production of carbon nanofibers and nanotubes several microns in length after the reaction. This indicates that the in situ reduced FeCo alloy catalysts more effectively promoted the growth of carbon nanofibers. These results could provide a viable strategy for future methane decomposition development aimed at producing hydrogen and high-value carbon. Full article

The state of the art in methane pyrolysis does not yet provide a definitive answer as to whether the concept of an elementary reaction is universally applicable to the apparently simple process of methane dissociation. Similarly, the literature currently lacks a comprehensive and unambiguous description of the methane pyrolysis process and, in particular, a single model that would well represent its course at both the micro and macro scales. Given the wide range of conditions under which this reaction can occur—whether thermal or thermo-catalytic, in solid or fluidized bed reactors—it is crucial to evaluate the usefulness of different kinetic models and their compatibility with basic thermodynamic principles and design assumptions. To address these research gaps, the authors analysed the thermodynamic and kinetic dependencies involved in the thermal decomposition of methane, using the synthesis of methane from its elemental components and its reversibility as a basis for exploring suitable kinetic models. Using experimental data available in the literature, a wide range of kinetic models have been analysed to determine how they all relate to the reaction rate constant. It was found that regardless of whether the process is catalytic or purely thermal, for temperatures above 900 °C the reversibility of the reaction has a negligible effect on the hydrogen yield. This work shows how the determined kinetic parameters are consistent with the Kinetic Compensation Effect (KCE) and, by incorporating elements of Transition State Theory (TST), the possibility of the existence of Entropy–Enthalpy Compensation (EEC). The indicated correspondence between KCE and EEC is strengthened by the calculated average activation entropy at isokinetic temperature $({∆S}_B=-275.0 \mathrm{J}·(\mathrm{m}\mathrm{o}\mathrm{l}·\mathrm{K}{)}^{-1}).$ Based on these results, the authors also show that changes in the activation energy $(E=20–421 \mathrm{k}\mathrm{J}·{\mathrm{m}\mathrm{o}\mathrm{l}}^{-1})$ can only serve as an estimate of the optimal process conditions, since the isoconversion temperature ($T_{iso}=1200-1450 \mathrm{K}>T_{eq}$) is shown to depend not only on thermodynamic principles but also on the way the reaction is carried out, with temperature (T) and pressure (P) locally compensating each other. Full article

A series of M(x)CoCeMgAlO mixed oxides with different transition metals (M = Cu, Fe, Mn, and Ni) with an M content x = 3 at. %, and another series of Fe(x)CoCeMgAlO mixed oxides with Fe contents x ranging from 1 to 9 at. % with respect to cations, while keeping constant in both cases 40 at. % Co, 10 at. % Ce and Mg/Al atomic ratio of 3 were prepared via thermal decomposition at 750 °C in air of their corresponding layered double hydroxide (LDH) precursors obtained by coprecipitation. They were tested in a fixed bed reactor for complete methane oxidation with a gas feed of 1 vol.% methane in air to evaluate their catalytic performance. The physico-structural properties of the mixed oxide samples were investigated with several techniques, such as powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX), elemental mappings, inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction under hydrogen (H₂-TPR) and nitrogen adsorption–desorption at −196 °C. XRD analysis revealed in all the samples the presence of Co₃O₄ crystallites together with periclase-like and CeO₂ phases, with no separate M-based oxide phase. All the cations were distributed homogeneously, as suggested by EDX measurements and elemental mappings of the samples. The metal contents, determined by EDX and ICP-OES, were in accordance with the theoretical values set for the catalysts’ preparation. The redox properties studied by H₂-TPR, along with the surface composition determined by XPS, provided information to elucidate the catalytic combustion properties of the studied mixed oxide materials. The methane combustion tests showed that all the M-promoted CoCeMgAlO mixed oxides were more active than the M-free counterpart, the highest promoting effect being observed for Fe as the doping transition metal. The Fe(x)CoCeMgAlO mixed oxide sample, with x = 3 at. % Fe displayed the highest catalytic activity for methane combustion with a temperature corresponding to 50% methane conversion, T₅₀, of 489 °C, which is ca. 40 °C lower than that of the unpromoted catalyst. This was attributed to its superior redox properties and lowest activation energy among the studied catalysts, likely due to a Fe–Co–Ce synergistic interaction. In addition, long-term tests of Fe(3)CoCeMgAlO mixed oxide were performed, showing good stability over 60 h on-stream. On the other hand, the addition of water vapors in the feed led to textural and structural changes in the Fe(3)CoCeMgAlO system, affecting its catalytic performance in methane complete oxidation. At the same time, the catalyst showed relatively good recovery of its catalytic activity as soon as the water vapors were removed from the feed. Full article

The current paper is devoted to the synthesis of ceria-supported nickel-based catalysts starting from different precursors of the nickel active phase. Thermal decomposition of metal-containing precursors, deposited onto stable supports by dry impregnation, belongs to the industrially preferred, simple ways of catalyst preparation. The synthesized series of NiO_x/CeO₂ catalysts have been tested in dry methane reforming (DMR), in which two greenhouse gases, i.e., CO₂ and CH₄, are simultaneously converted into syngas. Both reaction progress and stability of the catalyst strongly depend on nickel speciation, which in turn can be determined by the nature of the chosen precursor. Contrary to relatively many studies focused on the importance of synthetic methods and conditions on nickel speciation, the effect of precursor nature on structural, textural, and functional properties of catalytic systems has neither been discussed much nor fully understood. The main goal of this paper was to elucidate the effect of precursors on the properties of NiO_x/CeO₂. Consequences of the use of various nickel precursors (simple inorganic salts, organometallic complexes, and chelates) have been analyzed in detail from the viewpoint of their beneficial influence on the catalytic performance of NiO_x/CeO₂ system (containing 3 wt. % of Ni) tested in DMR. Full article

Dry reforming of methane (DRM) is gaining global attention due to its capacity to convert two greenhouse gases together. It proceeds through CH₄ decomposition over active sites (into CH_4−x) followed by CH_4−x oxidation by CO₂ (into syngas). Furthermore, CH_4−x oligomerization into coke cannot be neglected. Herein, xNi(5−x)Co/Pd+Al₂O₃ (x = 5, 3.75, 2.5, 1.25, 0) catalysts are prepared, investigated for DRM, and characterized with X-ray diffraction, UV-Vis, transmission electron microscopy, temperature-programmed reduction/desorption techniques, and thermogravimetry. Fine-tuning among stable active sites, graphitic carbon deposits, and catalytic activity is noticed. The total reducibility and basicity are found to decrease upon increasing the Co proportion up to 2.5 wt% in the Ni-Co bimetallic Pd+Al₂O₃-supported catalyst. The active sites derived from strong metal–support interaction species (NiAl₂O_x or dispersed CoO_x) are found to be promising in higher levels of activity. However, activity is, again, limited by graphitic carbon which is increased with an increasing Co proportion in the Ni-Co bimetallic Pd+Al₂O₃-supported catalyst. The incorporation of 1.25 wt% Co along with 3.75 wt% Ni over Pd+Al₂O₃ results in the generation of fewer such active sites, extensive oxidizable carbon deposits, and inferior catalytic activity compared to 5Ni/Pd+Al₂O₃. The 2.5Ni2.5Co/Pd+Al₂O₃ catalyst has lower crystallinity, a relatively lower coke deposit (than the 3.75Ni1.25Co/Pd+Al₂O₃ catalyst), and a higher number of stable active sites. It attains a 54–51% H₂ yield in 430 min TOS and 0.87 H₂/CO (similar to 5Ni/Pd+Al₂O₃) Full article

The article provides a short review on catalyst-based processes for the production of hydrogen starting from methane, both of fossil origin and from sustainable processes. The three main paths of steam- and dry-reforming, partial oxidation and thermo-catalytic decomposition are briefly introduced and compared, above all with reference to the latest publications available and to new catalysts which obey the criteria of lower environmental impact and minimize the content of critical raw materials. The novel strategies based on chemical looping with CO₂ utilization, membrane separation, electrical-assisted (plasma and microwave) processes, multistage reactors and catalyst patterning are also illustrated as the most promising perspective for CH₄ reforming, especially on small and medium scale. Although these strategies should only be considered at a limited level of technological readiness, research on these topics, including catalyst development and process optimization, represents the crucial challenge for the scientific community. Full article

Targeted synthesis of C/composite Ni-based material was carried out by the method of matrix isolation. The composite was formed with regard to the features of the reaction of catalytic decomposition of methane. The morphology and physicochemical properties of these materials have been characterized using a number of methods: elemental analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, temperature programmed reduction (TPR-H₂), specific surface areas (SSA), thermogravimetric analysis, and differential scanning calorimetry (TGA/DSC). It was shown by FTIR spectroscopy that nickel ions are immobilized on the polymer molecule of polyvinyl alcohol, and during heat treatment, polycondensation sites are formed on the surface of the polymer molecule. By the method of Raman spectroscopy, it was shown that already at a temperature of 250 °C, a developed conjugation system with sp2-hybridized carbon atoms begins to form. The SSA method shows that the formation of the composite material resulted in a matrix with a developed specific surface area of 20 to 214 m²/g. The XRD method shows that nanoparticles are essentially characterized by Ni, NiO reflexes. The composite material was established by microscopy methods to be a layered structure with uniformly distributed nickel-containing particles 5–10 nm in size. The XPS method determined that metallic nickel was present on the surface of the material. A high specific activity was found in the process of catalytic decomposition of methane—from 0.9 to 1.4 g_H2/g_cat/h, X_CH4, from 33 to 45% at a reaction temperature of 750 °C without the stage of catalyst preliminary activation. During the reaction, the formation of multi-walled carbon nanotubes occurs. Full article