Natural clay based nickel catalysts for dry reforming of methane: On the effect of support promotion (La,Al, Mn)

Fe modified natural clay supported Ni catalysts promoted with Lanthanum (La), aluminum (Al) and Manganese (Mn) were prepared by impregnation method. Calcined or reduced catalysts were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), H₂-temperature programmed reduction (H₂-TPR) and CO₂-temperature programmed desorption (CO₂-TPD). The addition of La, Al and Mn obviously affected the specific surface area and catalyst basicity. The presence of La, Al and Mn resulted in smaller Ni⁰ crystallite size and further promoted Ni dispersion. Al-promoted catalysts improved the Ni reducibility compared to La and Mn-promoted catalysts. After a reduction step at 900 °C, the studied catalysts have been tested in dry reforming of methane (DRM) from 850 to 600 °C. Al-promoted Fe-clay based catalysts presented the best catalytic performance in DRM. Both CH₄ and CO₂ conversions, and H₂/CO molar ratio followed the trend of thermodynamic calculations. Furthermore all conversions and H₂/CO molar ratio were close to theoretical values that were also forecasted by thermodynamics by means of HSC Chemistry 5.0.     

CuO/ZrO2 catalysts for water–gas shift reaction: Nature of catalytically active copper species

A series of CuO/ZrO₂ catalysts with different Cu loadings (4.1, 6.1 and 8.4 wt.%) were synthesized by a deposition-precipitation method and evaluated with the water–gas shift (WGS) reaction. In order to distinguish the different supported copper oxide species, (NH₄)₂CO₃-leaching process was conducted on the three CuO/ZrO₂ catalysts. The parent and leached catalysts were characterized by ICP-OES, XPS, XRD, N₂-physisorption, N₂O titration, UV–Vis DRS, H₂-TPR and CO-TPR. The results reveal that three types of copper oxide species are present on the parent CuO/ZrO₂ catalysts: (α) highly dispersed CuO that is weakly bound with ZrO₂; (β) strongly bound Cu-[O]-Zr species, which can not be leached by (NH₄)₂CO₃ solution and is possibly associated with the surface oxygen vacancy of ZrO₂; (γ) crystalline CuO. The XRD and TEM results of the freshly reduced catalysts disclose that the three types of CuO species are transformed into their corresponding metallic states after the H₂-pretreatment. It is found that the reaction rate correlates well with the amount of Cu-[O]-Zr species, indicating the metallic Cu derived from this species should be the catalytically active copper species for the WGS reaction. Moreover, CO-TPR results disclose that the Cu-[O]-Zr species play a significant role in promoting the reactivity of the surface hydroxyl groups, as is thought to be responsible for the high WGS activity of the CuO/ZrO₂ catalysts.     

Enhanced coke suppression by using phosphate-zirconia supported nickel catalysts under dry methane reforming conditions

Ni based phosphate zirconium catalysts were prepared by impregnation technique and used under CH₄ dry reforming conditions. Catalysts (x%Ni/8%PO₄–Zr, where x = 5, 10, 15 or 20) were characterized by nitrogen physical adsorption-desorption, X-ray diffraction, temperature programmed reduction, CO₂ and NH₃ temperature programmed desorption, thermal gravimetric analysis and transmission electron microscopy (TEM-EDAX). Catalysts displayed a typical mesoporous structure and different reducibility grade as a function of Ni loading, diagnostic of a different extent of metal-support interaction. Activity and stability strongly depend upon Ni loading while the best performance was observed for catalyst characterized by a Ni loading of 10 wt%. The CO₂-TPD profiles of spent catalysts indicated that such catalyst had more tendency to gasify coke formed over the catalyst surface. TGA analysis of used catalysts quantitatively showed that catalysts at higher Ni loading deactivated as result of huge graphitic carbon formation on catalyst surface. On the contrary, system 10%Ni8%PO₄/ZrO₂ turns out to be an excellent candidate to conduct the methane reforming reaction with CO₂ without coke formation at high CH₄ and CO₂ conversions. Phosphate play a fundamental role in promoting Ni–ZrO₂ interaction which reflects in the stabilization of catalytic system against metal sintering and coke formation.     

Enhanced ethanol steam reforming by CO2 absorption using CaO,CaO*MgO or Na2ZrO3

This paper presents results of thermodynamic analysis and experimental evaluation of hydrogen production by steam reforming of ethanol (SRE) combined with CO₂ absorption using a mixture of a solid absorbent (CaO, CaO*MgO and Na₂ZrO₃) and a Ni/Al₂O₃ catalyst. Thermodynamic analysis results indicate that a maximum of 69.5% H₂ (dry basis) is feasible at 1 atm, H₂O/C₂H₅OH = 6 (molar ratio) and T = 600 °C. whereas, the addition of a CO₂ absorbent at 1 atm, T = 600 °C and H₂O/C₂H₅OH/Absorbent = 6:1:2.5, produced a H₂ concentration of 96.6, 94.1, and 92.2% using CaO, CaO*MgO, and Na₂ZrO₃, respectively. SRE experimental evaluation achieved a maximum of 60% H₂. While combining SRE and a CO₂ absorbent exhibited a concentration of 96, 94, and 90% employing CaO, CaO*MgO, and Na₂ZrO₃, respectively at 1 atm, T = 600 °C, SV = 414 h⁻¹ and H₂O/C₂H₅OH/absorbent = 6:1:2.5 (molar ratio).     

Impact of Ce-Loading on Ni-catalyst supported over La2O3+ZrO2 in methane reforming with CO2

This paper investigated the effect of doping Ni supported catalysts with different ceria loading. The catalysts (5%Ni+x%Ce/La₂O₃+ZrO₂, where x = 0, 1, 2, 2.5, 3, 5) were synthesized via the wet impregnation technique and tested for methane reforming with carbon dioxide at atmospheric pressure, 700 °C and 42, 000 ml/g_cat.h gas hourly space velocity. The fresh catalysts were subjected to different characterization techniques such as X-ray diffraction, Surface area and pore analysis, H₂-temperature programmed reduction, CO₂-temperature programmed desorption and thermogravimetric analysis (TGA). A fine correlation between characterization results and catalytic activity is found. The results of the reactions indicated that 5%Ni/La₂O₃+ZrO₂ has the lowest conversion which increased with the percentage loading of CeO₂ up to 2.5 wt % and then began to decline. This suggests that 2.5 wt % loading is the optimum for CH₄ and CO₂ conversion. This particular catalyst composition has NiO species that could be reduced easily, as well as dense and wide distribution of all type of basic sites with respect to other catalyst system. The used catalysts were again subjected to TGA and RAMAN analysis where the least carbon deposition and the least deactivation factor was observed for 5%Ni+5%Ce/La₂O₃+ZrO₂ catalysts.     

Methane decomposition and carbon deposition over Ni/ZrO2 catalysts: Comparison of amorphous,tetragonal, and monoclinic zirconia phase

The influence of crystal phase of ZrO₂ on the catalytic performance of methane decomposition and the properties of deposited carbon on Ni/ZrO₂ catalysts was investigated. Ni/ZrO₂ catalysts were prepared by incipient-wetness impregnation method with 5% Ni loading, using amorphous, monoclinic, and tetragonal ZrO₂ as supports. It was found that Ni/am-ZrO₂ exhibited high activity and superior stability for carbon dioxide reforming of methane during 50 h of TOS, which could be attributed to the smaller Ni particle size and the lower coking rate. Additionally, the results of O₂-TPO/TPH/CO₂-TPO showed that the nature of carbon deposition via CH₄ decomposition on Ni/ZrO₂ catalysts was strongly influenced by both the Ni particle size and the crystal phase of zirconia. The lowest coking rate on Ni/am-ZrO₂ for carbon dioxide reforming of methane was due to the lower CH₄ decomposition rate and the higher gasification rate of carbon species by CO₂. Carbon deposited on Ni/am-ZrO₂ could be greatly removed by CO₂, due to the presence of large amount of adsorbed oxygen species on the surface of amorphous ZrO₂. For comparison, the imbalance of CH₄ cracking and removal of coke by CO₂ resulted in the accumulation of coke, leading to the deactivation of catalysts.     

Preparation of mesoporous nanocrystalline CuO–ZnO–Al2O3 catalysts for the H2 purification using catalytic preferential oxidation of CO (CO-PROX)

In this article, CuO–ZnO–Al₂O₃ catalysts with various copper contents were synthesized by a co-precipitation method and employed for the elimination of carbon monoxide from a mixture of 97% H₂, 1% CO and 2% O₂ at atmospheric pressure via carbon monoxide preferential oxidation (CO-PROX). The influence of the copper and zinc contents on the physicochemical characteristics and catalytic performance was investigated. The prepared samples were characterized using the N₂ adsorption-desorption (BET), X-ray diffraction (XRD), transmission and scanning electron microscopy (TEM and SEM) and temperature programmed reduction (TPR) techniques. The increment in CuO loading improved the activity of CuO–ZnO–Al₂O₃ catalysts for CO oxidation reaction. Among the prepared catalysts, the 50%CuO-3% ZnO-47% Al₂O₃ catalyst calcined at 400 °C with a BET area of 82.3 m²/g exhibited the best activity with a CO conversion of 88.9% at 125 °C. The effects of the presence of CO₂ and H₂O in the reaction feed stream and gas hourly space velocity (GHSV) were also studied.     

Enhanced performance of Ni catalysts supported on ZrO2 nanosheets for CO2 methanation: Effects of support morphology and chelating ligands

A series of Ni/ZrO₂ catalysts was prepared by the impregnation method with modification of the morphology of ZrO₂ support as well as the impregnation procedure and tested for CO₂ methanation. The catalysts supported on the ZrO₂ nanosheets displayed superior catalytic performance as compared with that on ZrO₂ nanoparticles, which could be mainly attributed to the abundant oxygen vacancies promoting the adsorption and dissociation of CO₂ molecules as well as the high dispersion of Ni species. With the introduction of ethylenediamine (En) in the impregnation procedure, the resulting Ni-15En/ZrO₂-1.5 catalyst showed the optimal activity with CO₂ conversion of 86% significantly higher than Ni/ZrO₂-0 of 44% and Ni/ZrO₂-1.5 of 79% at 0.5 MPa and 300 °C. The excellent performance was attributed to increased moderately basic sites for CO₂ adsorption in ZrO₂ nanosheets, as well as the enhanced dispersion of nickel caused by the complexation of Ni ions with En, which inhibited the aggregation of nickel particles in the subsequent thermal treatments. In conclusion, the synergistic effects of the morphology of ZrO₂ nanosheets as well as the chelating behavior of En contributed to the enhanced performance of Ni-15En/ZrO₂-1.5 in the CO₂ methanation reaction. The strategy shows good prospects for controlling the size of active metals, especially those that were dispersed on the surface of the two-dimensional (2D) metal oxide materials.     

High performance Ni exsolved and Cu added La0.8Ce0.2Mn0.6Ni0.4O3-based perovskites for ethanol steam reforming

La_0.8Ce_0.2Mn_0.6Ni_0.4O₃ with (LCMN@CuO) and without (LCMN) CuO addition are prepared by solution methods, followed by reduction in 5% H₂–N₂ stream at 650 °C to form Ni exsolved and CuO reduced catalysts, LCMN@Ni and LCMN@Ni/Cu, for ethanol (EtOH) steam reforming (ESR). The catalysts are characterized by X-ray diffraction (XRD), scanning and transmission electron microscopies (SEM and TEM), temperature programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy etc., and are evaluated for ESR with a steam/carbon ratio of 3 and a weight hourly space velocity (WHSV) of 4 h⁻¹ at temperatures between 500 and 700 °C. Ni exsolution and CuO reduction are confirmed on the substrates in LCMN@Ni and LCMN@Ni/Cu. Both the catalysts demonstrate a complete conversion of EtOH, forming mainly H₂, CO₂, CO and CH₄. And increasing temperature to 700 °C increases the yields of H₂ and CO to the levels about 90% and 40%, respectively, at the cost of CH₄; and such performance remains unchanged for 30 h. These results indicate that both LCMN@Ni and LCMN@Ni/Cu are promising catalysts for ESR, the main difference between them is that the latter is more chemically stable and more resistant to carbon deposition under ESR conditions.     

Syngas production by CO2 reforming of coke oven gas over Ni/La2O3–ZrO2 catalysts

Syngas production by CO₂ reforming of coke oven gas (COG) was studied in a fixed-bed reactor over Ni/La₂O₃–ZrO₂ catalysts. The catalysts were prepared by sol–gel technique and tested by XRF, BET, XRD, H₂-TPR, TEM and TG–DSC. The influence of nickel loadings and calcination temperature of the catalysts on reforming reaction was measured. The characterization results revealed that all of the catalysts present excellent resistance to coking. The catalyst with appropriate nickel content and calcination temperature has better dispersion of active metal and higher conversion. It is found that the Ni/La₂O₃–ZrO₂ catalyst with 10 wt% nickel loading provides the best catalytic activity with the conversions of CH₄ and CO₂ both more than 95% at 800 °C under the atmospheric pressure. The Ni/La₂O₃–ZrO₂ catalysts show excellent catalytic performance and anti-carbon property, which will be of great prospects for catalytic CO₂ reforming of COG in the future.     

Hydrogen production from oxidative steam reforming of methanol: Effect of the Cu and Ni impregnation on ZrO2 and their molecular simulation studies

Cu and Ni were supported on ZrO₂ by co-impregnation and sequential impregnation methods, and tested in the oxidative steam reforming of methanol (OSRM) reaction for H₂ production as a function of temperature. Surface area of the catalysts showed differences as a function of the order in which the metals were added to zirconia. Among them, the Cu/ZrO₂ catalyst had the lowest surface area. XRD patterns of the bimetallic catalysts did not show diffraction peaks of the Cu, Ni or bimetallic Cu–Ni alloys. In addition, TPR profiles of the bimetallic catalysts had the lowest reduction temperature compared with the monometallic samples. The reactivity of the catalysts in the range of 250–350 °C showed that the bimetallic samples prepared by successive impregnation had highest catalytic activity among all the catalysts studied. These results were also confirmed by theoretical calculations. The reactivity of the monometallic and bimetallic structures obtained by molecular simulation followed the next order: Ni_shellCu_core/ZrO₂ ≅ Cu_shellNi_core/ZrO₂ > Ni/Cu/ZrO₂ > Cu/Ni/ZrO₂ > Cu–Ni/ZrO₂ > Cu/ZrO₂ > Ni/ZrO₂. These findings agree with the experimental results, indicating that the bimetallic catalysts prepared by successive impregnation show a higher reactivity than the Cu–Ni system obtained by co-impregnation. In addition, the selectivity for H₂ production was higher on these catalysts. This result could be associated also to the presence of the bimetallic Cu–Ni and core–shell Ni/Cu nanoparticles on the catalysts, as was evidenced by TEM–EDX analysis, suggesting that the OSRM reaction may be a structure–sensitive reaction.     

Hydroxyl-promoter on hydrated Ni-(Mg,Si) attapulgite with high metal sintering resistance for biomass derived gas reforming

As hydrated magnesium-aluminum-silicate crystals, attapulgite and HNO₃/NaOH pretreated attapulgite were used as support to prepare nickel-based catalysts via ultrasonic-assisted impregnation method. The as-prepared catalysts were employed in the biomass derived gas (especially CO₂ and CH₄) reforming with a considerable catalytic performance achieved (CH₄ conversion: 75.26%, CO₂ conversion: 85.75%) over HNO₃-attapulgite (10% Ni) at 700 °C and GHSV of 36000 mL/g.h during 600 min, demonstrating the potential of modified attapulgite as support applied in catalytic reforming. According to the characterization results obtained from BET/FT-IR/H₂-TPR/XRD/SEM/TPO, it was found that the formation of (Ni, Mg) containing phyllosilicate improved metal sintering resistance by the confinement effect. Besides, FT-IR results illustrated the existence of hydroxyl in the catalyst structure, which was beneficial for inhibiting the Boudouard side reaction, further enhancing the carbon resistance of catalysts. Moreover, TPO results showed that the deposited carbon on modified attapulgite was mainly fibrous carbon which can be removed easily, thus maintaining the catalytic performance. Due to its unique structure and high metal sintering resistance, it is believed that the attapulgite supported catalyst can be used in any other catalytic reforming process such as steam reforming of methane.     

Zirconia supported nickel catalysts for glycerol steam reforming: Effect of zirconia structure on the catalytic performance

The effect of the zirconia structure in Ni/ZrO₂ catalysts on the glycerol steam reforming (GSR) reaction was studied. A tetragonal zirconia support was synthesized via a hydrolysis technique and loaded with 5 wt% Ni via a wet-impregnation method. Similarly, a commercial monoclinic zirconia support was also impregnated with 5 wt% Ni. Following calcination at 600 °C, physico-chemical properties of the prepared catalysts were investigated by X-Ray Diffraction (XRD), H₂-Temperature Programmed Reduction (H₂-TPR) and CO₂-Temperature Programmed Desorption (CO₂-TPD) techniques. The catalysts were then tested in the GSR reaction in the 400–700 °C range with a steam to glycerol molar ratio of 9:1 and a flow rate of 0.025 mL/min. The monoclinic catalyst exhibited a better performance giving higher hydrogen yields and glycerol conversions. This was attributed to an improved reducibility of Ni in this catalyst. Stability tests at 600 °C revealed the deactivation of the tetragonal catalyst during 6 h as a result of the formation of encapsulating coke which blocked active Ni metal sites. The monoclinic catalyst, exhibiting the formation of only filamentous coke, remained relatively stable for 24 h.     

Comparison of hydrogen consumption behavior of chromium and manganese promoted copper-based catalysts

CuO/ZnO/Al₂O₃/MgO–Cr and -Mn catalysts are synthesized using nitrate route via co-precipitation method. The precursors are characterized by XRD. The decomposition behavior of the precursors is analyzed by Air-TGA. The catalysts calcined at 250, 300, 350 and 450 °C are characterized by XRD and BET. CuO particle size reduction and surface area of the catalysts are investigated. Increasing the calcination temperature from 350 °C to 450 °C crystallite size increases about 3 nm, and BET surface area decreases about 30 m²/g. The reduction characteristics of the catalysts are analyzed via TPR and H₂-TGA, and H₂ consumption values of Cr and Mn containing catalysts is found as 40% and 60%, respectively. Peak temperatures of Mn containing catalysts (290–325 °C) are lower than peak temperatures of Cr containing catalysts (300–360 °C) as confirmed by H₂-TGA and H₂-DTG. The optimum H₂ consumption value of 52% is obtained with CuO/ZnO/Al₂O₃/MgO–Mn catalyst calcined at 350 °C.     

Combustion synthesis of copper catalysts for selective CO oxidation

Copper catalysts supported on ceria, zirconia and niobia were prepared by combustion method with urea, containing a CuO loading of 6 wt.%, and tested on selective oxidation of CO. The characterization of the samples by X-ray diffraction (XRD) presented the formation of solid solution on CuO–CeO₂ catalyst and a change in crystalline structure of the support with copper insertion on ZrO₂ and Nb₂O₅ catalysts. The analysis of temperature-programmed reduction (TPR) revealed different interaction degrees of copper with the supports, with reduction peaks between 222 and 390 °C. The temperature-programmed desorption of CO (TPD-CO) profiles showed formation of CO₂ and H₂ only for the ceria and zirconia catalysts. In relation to the catalytic tests, the CuO–CeO₂ catalyst presented the best performance, with CO conversion of 95% at 150 °C up to 45 h on stream, and CO₂ selectivity of 55%.     

Effect of boron doping and preparation method of Ni/Ce0.5Zr0.5O2 catalysts on the performance for steam reforming of ethanol

Ce_0.5Zr_0.5O₂ supported Ni-based catalysts with a Ni loading of 10 wt% and a B loading of 0.5 wt% were prepared by co-precipitation (assigned as NiCeZr(C) and BNiCeZr(C), respectively) and impregnation (assigned as NiCeZr(I) and BNiCeZr(I), respectively) procedures to evaluate the effects of fabrication methods and B-doped on the catalytic performance for steam reforming of ethanol (SRE). These catalysts were characterized with XRD, TPR, TPO, TEM, BET, TG and EA. The well dispersed active species that can be obtained through co-precipitation and formation of a NiB alloy come from a B-doped catalyst, which can promote catalysis performance and reaction pathway. Further, it can improve the selectivity of hydrogen for a SRE reaction. Also, the B-doped catalysts possess a high oxygen storage capacity (OSC) via formation of CeBO₃ under SRE ambience, which is the factor for removal of the carbonaceous species. TG and EA analyses demonstrate that there are fewer carbon deposits for the B-doped catalysts. The performance of the BNiCeZr(C) catalyst was preferential among these catalysts.     

Insight into the anti-coking ability of NiM/SiO2 (M=ZrO2, Ru) catalyst for dry reforming of CH4 to syngas

The development of Ni-based catalysts with outstanding anti-coking ability is necessary for realizing the industrial application of dry reforming of CH₄ (DRM) to syngas. Here, a facile combustion method with unique characteristic was employed to prepare the Ni/SiO₂ catalyst with different promoters (ZrO₂ or Ru). The effects of Ni particle size and promoter (ZrO₂ or Ru) on the anti-coking ability of Ni/SiO₂ catalyst were examined. The XRD and TEM results showed that improved Ni dispersion can be obtained via the facile combustion method, accompanying with enhanced metal-support interaction and CO₂ adsorption capacity confirmed by H₂-TPR and CO₂-TPD, respectively. In comparison with Ni-IMP catalyst (prepared via the traditional impregnation method), the carbon deposition over Ni–C catalyst (prepared via the combustion method) decreased by 67% (from 2.7 to 0.9 mg _{carbon deposition}·g^?1_CH4) as a result of the small Ni particles. The H₂-TPR and XPS results revealed the interaction between promoter (ZrO₂ and Ru) and Ni. The addition of ZrO₂ can enhanced the CO₂ activation ability of catalyst and the formed oxygen species can facilitate the elimination of carbon species, further decreasing the carbon deposition compared with Ni–C catalyst. The best catalytic performance with least carbon deposition (only 0.4 mg _{carbon deposition}·g^?1 _CH4) is achieved on the NiRu–C catalyst. The slower CH₄ dissociation rate and the improved CO₂ activation benefited from Ru can bring in the better balance between the carbon formation and elimination, leading to the best anti-coking ability of catalyst.     

The influence of Ni loading on coke formation in steam reforming of acetic acid

Steam reforming of acetic acid on Ni/γ-Al₂O₃ with different nickel loading for hydrogen production was investigated in a tubular reactor at 600 °C, 1 atm, H2O/HAc = 4, and WHSV = 5.01 g-acetic acid/g-cata.h^?1. The catalysts were characterized by temperature programmed oxidation (TPO) and differential thermal analysis (DTA), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The results showed that the amount of deposited carbidic-like carbon decreased and graphitic-like carbon increased with Ni loading increasing from 9 to 15 wt%. The Ni/γ-Al₂O₃ catalyst with 12 wt% Ni loading had higher catalytic activity and lower coke deposited rate.     

Cooperative role of cobalt and gallium under the ethanol steam reforming on Co/CeGaOx

The performance of gallium promoted cobalt-ceria catalysts for ethanol steam reforming (ESR) was studied using H₂O/C₂H₅OH = 6/1 mol/mol at 500 °C. The catalysts were synthetized via cerium-gallium co-precipitation and wetness impregnation of cobalt. A detailed characterization by N₂-physisorption, XRD, H₂-TPR and TEM allowed the normalization of contact time and rationalization of the role of each catalysts component for ESR. The gallium promoted catalyst, Co/Ce₉₀Ga₁₀O_x, was more efficient for the ethanol conversion to H₂ and CO₂, and the production of oxygenated by-products (such as, acetaldehyde and acetone) than Co/CeO₂. The catalytic performance is explained assuming that: (i) bare ceria is able to dehydrogenate ethanol to ethylene; (ii) Ce–O–Ga interface catalyzes ethanol reforming; (iii) both Ce–O–Co and Ce–O–Ga interfaces takes part in acetone production; and (iv) cobalt sites further allow C–C scission. It is suggested that a cooperative role between Co and Ce–O–Ga sites enhance the H₂ and CO₂ yields under ESR conditions.     

Effect of calcination conditions on time on-stream performance of Ni/La2O3–ZrO2 in low-temperature dry reforming of methane

A series of catalysts based on Ni supported on mesoporous La₂O₃–ZrO₂ was prepared and tested in low-temperature (400 °C) dry reforming of methane for 100 h on stream. The catalysts were obtained from the same precursor by calcining in either flowing air or Ar at different temperatures. Both the temperature and the atmosphere had an effect on the catalytic activity and on-stream stability. With increasing calcination temperature, the dispersion of Ni decreased. Surprisingly, this resulted not in the lower, but in the higher intrinsic activity of Ni species. This increase can be rationalized by assuming that the rate-determining step is not CH₄ decomposition, but the removal of carbon deposits from Ni particle by reaction with CO₂. The catalysts calcined at 800 °C in Ar and air showed the strongest and the second strongest deactivation, respectively, caused by the formation of crystalline carbon coatings due to a lower number of CO₂ adsorption sites. The size of Ni particles favoring the formation of layered carbon species was found to be the main origin of the catalysts deactivation in the low-temperature dry reforming of methane.