Ni–Re alloy catalysts on Al2O3 for methane dry reforming

Methane reforming with CO₂ is still of great interest due to growing demand creating a continuous need for new hydrogen sources. The main difficulty in this reaction is the deactivation of the catalyst due to the formation of carbon deposits on its surface. Herein, a series of commercial nickel catalysts supported on α-Al₂O₃ and modified with different amounts of rhenium (up to 4 wt%) was investigated. It was revealed that Re addition causes the formation of Ni–Re alloy during high temperature reduction, which was confirmed in deep XRD and STEM studies. The addition of Re positively influences not only the stability of the catalyst, but also increases its activity in the DRM reaction carried out in a Tapered Element Oscillating Microbalance (TEOM). The formation of Ni–Re alloy played a significant role in enhancing the properties of the catalyst.     

A comparative study of Ni catalysts supported on Al2O3, MgO–CaO–Al2O3 and La2O3–Al2O3 for the dry reforming of ethane

CO₂ utilization through the activation of ethane, the second largest component of natural and shale gas, to produce syngas, has garnered significant attention in recent years. This work provides a comparative study of Ni catalysts supported on alumina, alumina modified with CaO and MgO, as well as alumina modified with La₂O₃ for the reaction of dry ethane reforming. The calcined, reduced and spent catalysts were characterized employing XRD, N₂ physisorption, H₂-TPR, CO₂-TPD, TEM, XPS and TPO. The modification of the alumina support with alkaline earth oxides (MgO and CaO) and lanthanide oxides (La₂O₃), as promoters, is found to improve the dispersion of Ni, enhance the catalyst's basicity and metal-support interaction, as well as influence the nature of carbon deposition. The Ni catalyst supported on modified alumina with La₂O₃ exhibits a relatively stable syngas yield during 8 h of operation, while H₂ and CO yields decrease substantially for Ni/Al₂O₃.     

The effect of different atmosphere treatments on the performance of Ni/Nb–Al2O3 catalysts for methane steam reforming

Methane steam reforming is currently the most widely used hydrogen production reaction in industry today. Ni/Nb–Al₂O₃ catalysts were prepared by treatment under H₂, N_2, and air atmosphere prior to reduction and applied for methane steam reforming reaction at low temperature (400–600 °C). The hydrogen-treated catalysts increased catalytic activity, with 55.74% methane conversion at S/C = 2, GSVH of 14400 mL g^?1 h^?1 and 550 °C. The H₂ atmosphere treatment enhanced the Ni–Nb interaction and the formation of stable, tiny, homogeneous Ni particles (6 nm), contributing to good activity and stability. In contrast, the catalysts treated with nitrogen and air showed weaker interactions between Ni and Nb species, whereas the added Nb covered the active sites, which caused the decrease in activity. Meanwhile, carbon accumulation was also observed. This work is informative for preserving small nano-sized nickel particles to enhance catalytic performance.     

Synthetic gas production by dry reforming of methane over Ni/Al2O3–ZrO2 catalysts: High H2/CO ratio

Alumina prepared by the sol-gel method, was impregnated with zirconia (5, 15 and 30 wt.%). Subsequently, the resulting Al₂O₃–ZrO₂ supports were impregnated with 15% Ni to obtain the Ni/Al₂O₃–ZrO₂ catalysts. The obtained catalysts were characterized by BET, SEM, XRD, H₂-TPR and TPD- CO₂. The catalytic activity was studied by means of dry reforming of methane (DRM) for syngas production. The catalysts displayed different physicochemical properties and trends of their catalytic activity as a function of the ZrO₂ content in the mixed oxide supports. For instance, ZrO₂ (5 wt %) in the catalyst, led to enhanced concentration of the medium strength basic sites and increased specific surface area, yielding thus the best performance in the DRM, with low carbon deposition after 36 h of reaction, compared with the other catalysts. This indicates that during the DRM reaction, this catalyst can provide more surface oxygen to prevent carbon deposits that could deactivate the catalyst.     

Coke-resistance over Rh–Ni bimetallic catalyst for low temperature dry reforming of methane

Methane and carbon dioxide can be converted into syngas using the prospective dry reforming of methane technology. Carbon deposition is a major cause of catalyst deactivation in this reaction, especially at low temperature. The superior stability of bimetallic catalysts has made their development more and more appealing. Herein, a series of bimetallic RhNi supported on MgAl₂O₄ catalysts were synthesized and used for low temperature biogas dry reforming. The results demonstrate that the bimetallic RhNi catalyst can convert CH₄ and CO₂ by up to 43% and 52% over at low reaction temperature (600 °C). Moreover, the reaction rate of CH₄ and CO₂ of RhNi–MgAl₂O₄ remains stable during the 20 h long time stability test, most importantly, there was no obviously carbon deposition observed over the spent catalyst. The enhanced coking resistance should be attributed to the addition of a little amount of noble metal Rh can efficiently suppress dissociation of CH_X1 species into carbon, and the high surface areas of MgAl₂O₄ support can also promote the adsorption and activation of carbon dioxide to generate more O1 species. Balancing the rate of methane dissociation and carbon dioxide activation to inhibit the development of carbon deposition is a good strategy, which provides a guidance for design other high performance dry reforming of methane catalysts.     

Co–Ni/WC-AC catalysts for dry reforming of methane: The role of Ni species

To improve the DRM reaction performance of the catalysts, a series of Co–Ni/WC-AC catalysts are prepared by impregnation using WC-AC as the support. The structural features of the fresh and spent catalysts are characterized by BET, XRD, H₂-TPR, XPS and TG. The results show that the introduction of Ni in the 20Co/WC-AC catalyst promotes the conversion of W species to WC. Further, WC enhances the interaction between the active metal and the support. Thus, the activity and sintering resistance of Co–Ni/WC-AC catalysts are improved. It is also found that the introduction of different ratios of Ni has a significant effect on the chemical environment (oxygen environment) on the catalyst surface.10Co–10Ni/WC-AC catalysts showed high surface O_α and O_β contents of 26% and 53%, respectively. The catalyst shows excellent catalytic performance. The conversion of CH₄ and CO₂ is stable at about 84% and 85% at 800 °C.     

Dry reforming of methane over Ni/MgO–Al2O3 catalysts: Thermodynamic equilibrium analysis and experimental application

In this study, dry reforming of methane (DRM) employing a Ni/MgO–Al₂O₃ catalyst was undertaken to evaluate the effects of temperature (650, 700 and 750 °C), weight hourly space velocity (7.5, 15 and 30 L h⁻¹ g_cat⁻¹) and catalyst MgO content (3, 5 and 10 wt%) on catalytic activity and coke-resistance. The catalysts were prepared by the wet impregnation method and were characterized by wavelength dispersive X-ray fluorescence (XRF), N₂ physisorption, X-ray diffraction (XRD), temperature-programmed reduction (TPR-H₂), temperature-programmed desorption (TPD-NH₃), H₂ chemisorption, thermogravimetric/derivative thermogravimetry analysis (TG/DTG) and scanning electron microscopy (SEM). The best conversions of methane (CH₄) and carbon dioxide (CO₂) and lower coke formation were obtained using higher temperatures, lower WHSV and 5 wt% MgO in the catalyst. The H₂/CO molar ratios obtained were within the expected range for the DRM reaction. The experimental yields of H₂ and CO differed from chemical equilibrium, mainly due to occurrence of the reverse water-gas shift reaction. Thermodynamic analysis of the reaction system, based on minimization of the Gibbs free energy, was performed in order to compare the experimental results with the optimal values for chemical equilibrium conditions, which has indicated that the DRM reaction was favored by higher temperature, lower pressure, and lower CH₄/CO₂ molar ratio.     

Anti-sintering mesoporous Ni–Pd bimetallic catalysts for hydrogen production via dry reforming of methane

In this work, a series of mesoporous silica supported nickel or nickel-palladium catalysts were synthesized and performed in dry reforming of methane (DRM) reaction for producing syngas. Compared with the monometallic catalyst, the Ni–Pd bimetallic catalysts, especially synthesized by the OA-assisted route, exhibited promising yields of H₂ and CO in the catalytic DRM reaction, achieved at 63% and 69% over NiPd-SP-OA bimetallic catalyst at the reaction temperature of 700 °C, respectively. TEM image results confirmed that no obvious sintering phenomenon happened on spent NiPd-SP-OA bimetallic catalyst within 1550 min time-on-stream reaction. Based on the results of XRD, XPS and H₂-TPR, it could be known that the superior catalytic performance on NiPd-SP-OA catalyst were main ascribed to the smaller-sized Ni nanoparticles with a uniform metal dispersion and a larger fraction of exposed active sites (Ni⁰).     

Mixed reforming of methane over Ni–K/CeO2–Al2O3: Study of catalyst performance and reaction kinetics

Syngas can be effectively produced by mixed reforming of methane (MRM). In this work, the performance of Ni–K/CeO₂–Al₂O₃ catalyst in this process was investigated in a fixed-bed reactor in the 923–1073 K range. Both potassium and ceria are renowned for improving the performance of Ni catalyst in the reforming process. The influence of reaction conditions (viz. temperature, space time, feed composition and time-on-stream) on the conversion of two reactants CH₄ and CO₂, yield of the products H₂ and CO and the H₂/CO ratio in syngas were studied. At T = 1073 K and W/Q₀ = 0.17 g-h/L (here, W and Q₀ denote catalyst mass and volumetric flow rate of feed), conversions of CH₄ and CO₂ were 91.2 and 80.1%. When S/C ratio (or steam-to-carbon ratio) in feed increased from 0.2 to 0.5 mol/mol, H₂/CO ratio at T = 1073 K changed from 1.32 to 2.14 mol/mol. The catalyst performed stably for 50 h of time-on-stream. Reaction kinetics was studied between 973 and 1073 K and power law kinetic model was suggested. The apparent activation energy values for consumption of CH₄ and CO₂ were found to be 33.3 and 45.5 kJ/mol, respectively. This work is expected to aid catalyst development and reactor design for the MRM process.     

Highly coke resistant Ni–Co/KCC-1 catalysts for dry reforming of methane

Nanofibrous KCC-1 supported Ni–Co bimetallic catalysts were investigated for dry reforming of methane for syngas generation. Monometallic catalysts such as Ni/KCC-1 and Co/KCC-1, and a series of bimetallic Ni–Co/KCC-1 catalysts were prepared by impregnation and co-impregnation method, respectively. All the catalysts were characterized by XRD, FT-IR, HR-SEM, FE-SEM, XPS, FT-Raman, BET, UV–Visible DRS and AAS techniques. Monometallic nickel supported catalyst contains NiO as an active phase, whereas bimetallic nickel catalysts contain Ni₂O₃, and NiCo₂O₄ on the surface. In the case of cobalt loaded catalysts, spinel Co₃O₄ is the dominant active species, apart from NiCo₂O₄. The addition of cobalt in Ni/KCC-1 has a pronounced effect on the crystallite size, surface area and active species. The hydrogen pretreatment of the catalyst produces bimetallic Ni–Co alloy on the surface. The catalytic activities of the bimetallic catalysts towards dry reforming of methane are better than monometallic catalysts. Mesoporous silica-based KCC-1 offers easy accessibility to the entire surface moieties due to its fibrous nature and the presence of channels, instead of pores. The 2.5%Ni-7.5%Co/KCC-1 showed the maximum CH₄ and CO₂ conversion along with a remarkably low H₂/CO ratio. The life-time test confirms the high thermal stability of the catalysts at 700 °C for 8 h, with less deactivation due to coke formation. The spent catalysts were characterized by XRD, TGA, FT-Raman, and FE-SEM to understand the structural and chemical changes during the reaction. The insignificant D band and G band of graphitic carbon in FT-Raman spectra for the highly active 2.5%Ni-7.5%Co/KCC-1 and 5%Ni–5%Co/KCC-1 catalysts along with TGA results containing 12% weight loss confirms the minimum coke deposition, formation of amorphous carbon and highest coke resistance. The fibrous support restricts the sintering and aggregation of nickel particles as well the deposition of coke. The addition of amphoteric cobalt increases the activity and stability of the catalysts. Ni–Co/KCC-1 with high coke resistance seems to be a promising catalyst for dry reforming of methane.     

Paper-structured catalyst containing CeO2–Ni flowers for dry reforming of methane

In this paper, ceria flowers containing nano-sized catalyst Ni particles were prepared on alumina-silica fiber network for production of hydrogen from biogas. The CeO₂ flowers were prepared using hydrothermal method and then NiO was loaded on the CeO₂ flowers by impregnation method. The Paper-structured catalysts (PSCs) were prepared from alumina-silica fibers and the CeO₂–NiO flowers using conventional paper making method. The loaded NiO particles were uniformly dispersed on the CeO₂ flowers with the use of polyvinylpyrrolidone as a dispersion enhancer, which was observed by FE-SEM and EDX analysis. The NiO particles were then reduced into Ni by using H₂. The PSCs containing CeO₂–Ni flowers with various Ni contents (2.1, 3.4, and 4.6%) were used for dry reforming of CH₄. It was found that 3.4% amount of Ni on the PSC was suitable for reforming reaction, and the higher amount of Ni (4.6%) did not increase the CH₄ conversion. The PSC with the CeO₂ flowers had porous structure and large surface area leading to the better dispersion of the Ni particles with smaller size. This helped increase in catalytic performance, prevention of agglomerated particle catalysts at high temperature and coke forming after a long time operation. The CH₄ conversion of the PSCs containing CeO₂–NiO flowers in the dry reforming of CH₄ was much higher (nearly 90%) with a smaller Ni content in comparison with the PSC without the CeO₂ flowers (with higher Ni content of 8.6%). Moreover, the PSCs with the flowers exhibited an excellent catalytic stability with the degradation of CH₄ conversion of only 3.1% after 50 h of reforming. In addition, the high oxygen storage capacity and oxygen mobility of CeO₂ resulted in a partial removal of coke forming on the catalyst particles during reforming. This indicated that the catalytic activity of the Ni particles dispersed on the CeO₂ flowers for dry reforming of CH₄ was superior to that of various Ni-based catalyst systems which had much higher Ni contents. Therefore, it is possible to use the PSCs containing CeO₂–Ni flowers to generate hydrogen for use as fuels from dry reforming of CH₄.     

Effects of CaO addition on Ni/CeO2–ZrO2–Al2O3 coated monolith catalysts for steam reforming of N-decane

A series of 10 wt%Ni/CeO₂–ZrO₂–Al₂O₃ (10%Ni/CZA) coated monolith catalysts modified by CaO with the addition amount of 1 wt%~7 wt% are prepared by incipient-wetness co-impregnation method. Effects of CaO promoter on the catalytic activity and anti-coking ability of 10%Ni/CZA for steam reforming of n-decane are investigated. The catalysts are characterized by N₂ adsorption-desorption, XRD, SEM-EDS, TEM, NH₃-TPD, XPS, H₂-TPR and Raman. The results show that specific surface area and pore volume of as-prepared catalysts decrease to some extent with the increasing addition of CaO. However, the proper amounts of CaO (≤3 wt%) significantly enhance the catalytic activity in terms of n-decane conversion and H₂ selectivity mainly due to the improved dispersion of NiO particles (precursor of Ni particles). As for anti-coking performance, reducibility of CeO₂ in composite oxide support CZA is promoted by CaO resulting in providing more lattice oxygen, which favors suppressing coke formation. Moreover, the addition of CaO reduces the acidity of 10%Ni/CZA, especially the medium and strong acidity. But far more importantly, a better dispersion of NiO particles obtained by proper amounts of CaO addition is dominant for the lower carbon formation, as well as the higher catalytic activity. For the spent catalysts, amorphous carbon is the main type of coke over 10%Ni–3%CaO/CZA, while abundant filamentous carbon is found over the others.     

Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts

A series of Ni–Ce–Al composite oxides with various Ni molar contents were synthesized via the refluxed co-precipitation method and used for natural gas reforming of CO₂ (NGRC) for syngas production. The effect of Ni molar content, reaction temperature, feed gas ratio and gas hourly space velocity (GHSV) on the Ni–Ce–Al catalytic performance was investigated. The Ni₁₀CeAl catalyst was selected to undergo 30 h stability test and the conversion of CH₄ and CO₂ decreased by 2.8% and 2.6%, respectively. The characterization of the reduced and used Ni₁₀CeAl catalyst was performed using BET, H₂-TPR, in-situ XRD, TEM, and TGA-DTG techniques. The in-situ XRD results revealed that Ce₂O₃, CeO₂ and CeAlO₃ coexisted in the Ni₁₀CeAl catalyst after reduction at 850 °C for 2 h. The results of the TEM analysis revealed that the Ni particle size increased after the NGRC reaction, which mainly caused the catalyst deactivation.     

High performance of Mg–La mixed oxides supported Ni catalysts for dry reforming of methane: The effect of crystal structure

A series of mixed Mg–La oxide supports with various Mg²⁺/La³⁺ mole ratios were prepared via co-precipitation of Mg and La nitrates, and then impregnated to form 5 wt.% Ni catalysts. The as-prepared catalysts were evaluated in DRM reaction for 200 h and characterized by means of in situ DRIFTS, XRD, TEM, CO₂-TPD, XPS, and TGA. It was found that the interaction of suitable amount of MgO with La₂O₃ stabilized cubic La₂O₃ species in catalysts, which has high basicity to adsorb CO₂ forming monoclinic La₂O₂CO₃ (Ia) species in DRM reaction. The introduction of MgO also created surface oxygen ions (i.e. O^–). Both monoclinic La₂O₂CO₃ (Ia) and surface oxygen species are able to oxidize and remove deposited carbon, keeping the Ni catalyst at high activity and stability. Low Mg²⁺/La³⁺ ratios generated hexagonal La₂O₃ and La₂O₂CO₃ (II) in DRM reaction. The hexagonal La₂O₂CO₃ (II) did not play significant role in carbon removal so that the catalysts deactivated fast.     

Influence of metal-support interactions on reaction pathways over Ni/CeZrOx–Al2O3 catalysts for ethanol steam reforming

This work investigates selective Ni locations over Ni/CeZrO_x–Al₂O₃ catalysts at different Ni loading contents and their influences on reaction pathways in ethanol steam reforming (ESR). Depending on the Ni loading contents, the added Ni selectively interacts with CeZrO_x–Al₂O₃, resulting in the stepwise locations of Ni over CeZrO_x–Al₂O₃. This behavior induces a remarkable difference in hydrogen production and coke formation in ESR. The selective interaction between Ni and CeZrO_x for 10-wt.% Ni generates more oxygen vacancies in the CeZrO_x lattice. The Ni sites near the oxygen vacancies enhance reforming via steam activation, resulting in the highest hydrogen production rate of 1863.0 μmol/g_cat·min. In contrast, for 15 and 20-wt.% Ni, excessive Ni is additionally deposited on Al₂O₃ after the saturation of Ni–CeZrO_x interactions. These Ni sites on Al₂O₃ accelerate coking from the ethylene produced on the acidic sites, resulting in a high coke amount of 19.1 mg_c/g_cat·h (20Ni/CZ-Al).     

Eclectic trimetallic Ni–Co–Ru catalyst for the dry reforming of methane

Ru-promoted Ni–Co catalysts supported on MgO–Al₂O₃ are tested for dry reforming activity in a fixed-bed reactor at atmospheric pressure. The effect of temperature and contact time is investigated, and the catalysts maintain high stability for up to 47 h on stream. The support surface area significantly affects dispersion, and whisker carbon is observed in spent samples with pore sizes higher than 15 nm. H₂-TPR studies reveal the presence of spinels that are not completely reducible, yet the catalysts give remarkable activity. Four synthesis methods are tested for the support, with the sol-gel method in neutral conditions providing the best performance, with a small compromise on activity but a significant improvement in catalyst stability and no whisker carbon formation. Further work will optimize the Ni/Co ratio in the active phase to decrease the carbon buildup on the catalysts.     

Impact of ceria over WO3–ZrO2 supported Ni catalyst towards hydrogen production through dry reforming of methane

ZrO₂ supported Nickel catalyst, 9 wt%WO₃ -91 wt%ZrO₂ supported Nickel catalyst and ceria promoted 9 wt%WO₃-91 wt%ZrO₂ supported Nickel catalyst (5NixCe/WZr catalyst) is synthesized via wet impregnation and characterized by XRD, UV–vis, CO₂ -TPD, H₂ TPR-CO₂ TPD-H₂ TPR cycle, TPH, TPH followed by O₂ -TPO and CO₂ -TPD followed by O₂ -TPO. Due to limitation in surface re-oxidizing capability and shading of catalytic active sites by thermally stable carbonates; catalytic activity of unpromoted catalyst system is less. 5NixCe/WZr catalyst has extended CH₄ decomposition sites, additional basic sites (during the reaction) for CO₂ adsorption and excellent redox accompany (Ce ⁺⁴/Ce ⁺³, W+⁶/W ⁺⁴) for carbon oxidation and re-oxidizing capability of surface up to the pristine level. 2.5 wt% Ceria promotional addition is resulted into 78% H₂ yield constantly up to 420 min TOS. The carbon deposit over ceria promoted system (up to 2.5 wt%) is amorphous type, more easily/moderately reducible, oxidizable and removable.     

Combined steam and CO2 reforming of methane (CSCRM) over Ni–Pd/Al2O3 catalyst for syngas formation

In order to syngas formation, combined steam and carbon dioxide reforming of methane (CSCRM) used in the presence of Ni–Pd/Al₂O₃ catalysts, which were synthesized by the sol-gel method. Al₂O₃ supported Ni–Pd catalyst exhibited the appropriate surface area of 176.2 m²/g and high dispersion of NiO phase with an average crystallite size of 11 nm, which was detected on catalyst surface utilizing transmission electron microscopy (TEM). The influence of three independent operating parameters including reaction temperature in the range of 500–1000 °C; (CO₂ + H₂O)/CH₄ ratio, in the range of 1–3 and CO₂/H₂O ratio; in the range of 1–3, were investigated on the responses (i.e., CH₄ conversion, H₂ yield, CO yield, amount of coke formation on the catalyst surface and H₂/CO ratio) in CSCRM by using response surface methodology–central composite design (RSM-CCD) method. The obtained results from ANOVA and the proposed quadratic models could fine forecast the responses. It was seen that the total methane conversion and CO yield was almost accessible at temperatures higher than 850 °C. Moreover, the CO₂/H₂O ratio exhibited no significant effect on the CH₄ conversion, H₂ yield and CO yield of Ni–Pd/Al₂O₃ catalysts in CSCRM reaction. However, the high CO₂/H₂O ratio in inlet feed led to the syngas formation with a low H₂/CO ratio. The results revealed that lower CO₂/H₂O ratio and higher temperature as well as higher (CO₂ + H₂O)/CH₄ ratio help to decrease the coke formation.     

Thermocatalytic decomposition of methane over mesoporous nanocrystalline promoted Ni/MgO·Al2O3 catalysts

Thermocatalytic decomposition of CH₄ is an interesting method for the production of hydrogen. In this article, the catalytic and structural properties of the La, Ce, Co, Fe, and Cu-promoted Ni/MgO·Al₂O₃ catalysts were investigated in the thermal decomposition of CH₄. Mesoporous MgO·Al₂O₃ powder with the high BET area (>250 m²/g) was synthesized by a novel and simple sol–gel method. The different instrumental methods (XRD, BET, SEM, H₂-TPR and TPO) were used for evaluating the physicochemical characteristics of the samples. The addition of Cu to Ni/MgO·Al₂O₃ dramatically improved the catalytic performance and the Cu-promoted catalysts exhibited the highest CH₄ conversion and H₂ yields among the promoted and unpromoted catalysts. The Cu-promoted catalyst possessed the highest stability in CH₄ conversion during 10 h of reaction. The results also indicated that the Ni–Cu/MgO·Al₂O₃ catalyst with 15 wt.% Cu showed the highest catalytic activity and stability at higher temperatures (>80% CH₄ conversion).     

Improved hydrogen production performance of Ni–Al2O3/CaO–CaZrO3 composite catalyst for CO2 sorption enhanced CH4/H2O reforming

Bifunctional composite catalysts are very intrigued to produce hydrogen via CO₂ sorption enhanced CH₄/H₂O reforming. However, their hydrogen production performance declined over multiple cycles, owing to the structure collapse and the sintering of active component under high-temperature regeneration. This work reported the facile synthesis of long-lasting Ni–Al₂O₃/CaO–CaZrO₃ composite catalysts with less inert components (36 wt%) for stable hydrogen production over the multiple cycles of CO₂ sorption enhanced CH₄/H₂O reforming. The effects of reaction and regeneration temperature on the hydrogen production performance of Ni–Al₂O₃/CaO–CaZrO₃ were explored. Ni–Al₂O₃/CaO–CaZrO₃ demonstrated high activity and stability while fixing reaction temperature as 600 °C and regeneration temperature as 750 °C. Of particular importance, H₂ concentration was 98 vol% even after 10 hydrogen production cycles due to the inert component CaZrO₃ having a cross-linked structure. The distribution of CaZrO₃ in the composite as a coral-like structure inhibited the sintering of CaO through high Taman temperature and physical separation. Moreover, it provided the skeleton support and pore volume for the repeated expansion and contraction process of CaO to CaCO₃ during the cycling process. Finally, the sintering of Ni slowed down in appropriate regeneration temperature to maintain the structure of the composite catalyst, which further improved the catalyst's stability over multiple cycles.