Mesoporous nanocrystalline ceria–zirconia solid solutions supported nickel based catalysts for CO2 reforming of CH4

A series of mesoporous nanocrystalline ceria–zirconia solid solutions with different Ce/Zr ratios were facilely synthesized via improved evaporation induced self-assembly strategy. The obtained materials with advantageous structural properties and excellent thermal stabilities were characterized by various techniques and investigated as the supports of the Ni based catalysts for CO₂ reforming of CH₄. The effects of Ce/Zr ratio and mesopore structure on promoting catalytic performances had been investigated. It was found that the catalyst supported on carrier with 50/50 Ce/Zr ratio behaved the highest catalytic activity. The reason for this might be that the mesoporous ceria–zirconia solid solution carrier contributed to the activation of CO₂ by its own redox property. Compared with the catalyst without obvious mesostructure, the current mesoporous catalyst performed higher catalytic activity and better catalytic stability, demonstrating the advantages of the mesostructure. On the one hand, the predominant textural properties such as large surface area, big pore volume, and uniform channel helped to the high dispersion of the Ni particles among the mesoporous framework, finally leading to higher catalytic activity. On the other hand, the mesoporous matrix could stabilize the Ni nanoparticles under severe reduction and reaction conditions by the “confinement effect”, committed to better catalytic stability. Besides, the properties of the coke over the mesoporous catalyst were also carefully studied. Generally, these mesoporous nanocrystalline ceria–zirconia solid solutions were a series of promising catalytic carriers for CO₂ reforming of CH₄.     

Effects of noble metal-doping on Ni/La2O3–ZrO2 catalysts for dry reforming of coke oven gas

A series of noble metal (Ru, Pd, Ag) doped Ni catalysts supported on La₂O₃–ZrO₂ mixed oxide were prepared using the sol–gel method and evaluated for use in dry reforming of coke oven gas (COG). The catalysts were investigated by means of N₂ adsorption–desorption, XRD, H₂-TPR, TPH, TEM and TG–DSC. TPH analysis revealed that two carbonaceous species formed on the used catalysts and that the low-temperature carbon species was sufficiently active for the reforming reaction. TEM observations indicated that highly dispersed and small metal particles were formed, suppressing coke deposition and improving catalytic performance. The test results indicated that the addition of trace amounts of noble metals effectively promotes catalytic activity. The 0.1Ru–10Ni/8LZ catalyst showed the highest performance among the bimetallic catalysts, because of the strong synergetic effect between Ru and Ni via the formation of a Ru–Ni alloy, which will be promising catalysts in the catalytic dry reforming of COG.     

Hydrogen production by auto-thermal reforming of ethanol over Ni catalysts supported on ZrO2: Effect of preparation method of ZrO2 support

Zirconia supports were prepared by a sol–gel method (S-ZrO₂) and by a templating sol–gel method (M-ZrO₂). Nickel catalysts supported on zirconia were then prepared by an incipient wetness impregnation method for use in hydrogen production by auto-thermal reforming of ethanol. For comparison, a commercial zirconia (C-ZrO₂) was also employed as a support for nickel catalyst. The effect of preparation method of zirconia on the catalytic property and catalytic performance of supported nickel catalysts (Ni/C-ZrO₂, Ni/S-ZrO₂, and Ni/M-ZrO₂) was investigated. The crystalline and physical property of zirconia supports and the catalytic performance of supported nickel catalysts were strongly affected by the preparation method of zirconia. BET surface area and pore volume were decreased in the order of M-ZrO₂ > S-ZrO₂ > C-ZrO₂. Both M-ZrO₂ and S-ZrO₂ supports showed only tetragonal phase of ZrO₂, while C-ZrO₂ support exhibited tetragonal and monoclinic phases of ZrO₂. Crystalline size of nickel species in the Ni/ZrO₂ catalysts decreased with increasing surface area and pore volume of ZrO₂ supports. All the Ni/ZrO₂ catalysts exhibited 100% conversion of ethanol at 500 °C, while product distributions over the Ni/ZrO₂ catalysts were different depending on the preparation method of zirconia. Among the catalysts tested, the Ni/M-ZrO₂ catalyst showed the best catalytic performance in hydrogen production by auto-thermal reforming of ethanol. Well developed mesopore, high surface area, and pure tetragonal phase of ZrO₂ were responsible for fine nickel dispersion and high catalytic performance of Ni/M-ZrO₂. C–C bond cleavage reaction and methane steam reforming reaction were also accelerated over the Ni/M-ZrO₂ catalyst.     

Effects of modifying Ni/Al2O3 catalyst with cobalt on the reforming of CH4 with CO2 and cracking of CH4 reactions

Alumina supported nickel (Ni/Al₂O₃), nickel–cobalt (Ni–Co/Al₂O₃) and cobalt (Co/Al₂O₃) catalysts containing 15% metal were synthesized, characterized and tested for the reforming of CH₄ with CO₂ and CH₄ cracking reactions. In the Ni–Co/Al₂O₃ catalysts Ni–Co alloys were detected and the surface metal sites decreased with decrease in Ni:Co ratio. Turnover frequencies of CH₄ were determined for both reactions. The initial turnover frequencies of reforming (TOF_DRM) for Ni–Co/Al₂O₃ were greater than that for Ni/Al₂O₃, which suggested a higher activity of alloy sites. The initial turnover frequencies for cracking (TOF_CRK) did not follow this trend. The highest average TOF_DRM, H₂:CO ratio and TOF_CRK were observed for a catalyst containing a Ni:Co ratio of 3:1. This catalyst also had the maximum carbon deposited during reforming and produced the maximum reactive carbon during cracking. It appeared that carbon was an intermediate product of reforming and the best catalyst was able to most effectively crack CH₄ and oxidize carbon to CO by CO₂.     

Hydrogen production by auto-thermal reforming of ethanol over nickel catalyst supported on metal oxide-stabilized zirconia

Metal oxide-stabilized mesoporous zirconia supports (M–ZrO₂) with different metal oxide stabilizer (M = Zr, Y, La, Ca, and Mg) were prepared by a templating sol–gel method. 20 wt% Ni catalysts supported on M–ZrO₂ (M = Zr, Y, La, Ca, and Mg) were then prepared by an incipient wetness impregnation method for use in hydrogen production by auto-thermal reforming of ethanol. The effect of metal oxide stabilizer (M = Zr, Y, La, Ca, and Mg) on the catalytic performance of supported nickel catalysts was investigated. Ni/M–ZrO₂ (M = Y, La, Ca, and Mg) catalysts exhibited a higher catalytic performance than Ni/Zr–ZrO₂, because surface oxygen vacancy of M–ZrO₂ (M = Y, La, Ca, and Mg) and reducibility of Ni/M–ZrO₂ (M = Y, La, Ca, and Mg) were enhanced by the addition of lower valent metal cation. Hydrogen yield over Ni/M–ZrO₂ (M = Zr, Y, La, Ca, and Mg) catalyst was monotonically increased with increasing both surface oxygen vacancy of M–ZrO₂ support and reducibility of Ni/M–ZrO₂ catalyst. Among the catalysts tested, Ni catalyst supported on yttria-stabilized mesoporous zirconia (Ni/Y–ZrO₂) showed the best catalytic performance.     

Hydrogen production by catalytic decomposition of selected hydrocarbons and H2O dissociation over CeZrO2 and Ni/CeZrO2

Presented paper deals with the catalytic decomposition of hydrocarbons (methane and toluene) in the aspect of H₂ production and types of obtained carbon deposits. The catalyst used in our studies was nickel supported on ceria–zirconia (Ni/CeZrO₂). The aim of this work was to investigate the reactivity of obtained carbon deposits with H₂O. Both issues are of great importance for determining the mechanisms of carbon deposits formation and their suppression during steam reforming reaction.     

Biogas reforming for hydrogen production over nickel and cobalt bimetallic catalysts

Ni/Co bimetallic catalysts supported by commercial γ-Al₂O₃ modified with La₂O₃ for biogas reforming were prepared by conventional incipient wetness impregnation. The catalysts were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), BET surface area and porosity analysis (BET), H₂ temperature-programmed reduction (H₂-TPR), transmission electron microscopy (TEM) and thermogravimetry coupled to differential scanning calorimetry (TG–DSC). XRD and XPS analysis revealed that a Ni/Co alloy was formed in the bimetallic catalysts. The Ni/Co ratio could be adjusted to improve pore textural properties, which enhanced the metal particle dispersion and resulted in smaller metal particle size, and thus increased the catalytic activity and resistance to carbon deposition. The activity and stability of the catalysts for biogas reforming was tested at 800 °C, ambient pressure, GHSV of 6000 ml g_cat⁻¹ h⁻¹ and a CH₄/CO₂ molar ratio of 1 without dilute gas. Experimental results showed that the catalytic activity could be closely related to the Ni/Co ratio. The bimetallic catalyst 7Ni3Co/LaAl exhibited better catalytic and anti-coking performance due to smaller metal particles, higher metal dispersion, uniform pore distribution, surface enrichment of Co, as well as the synergetic effect between Ni and Co. During a 290 h stability test over the catalyst 7Ni3Co/LaAl, the average conversion of CH₄ and CO₂, selectivity to H₂ and CO, and ratio of H₂/CO were 93.7%, 94.0%, 94.9%, 97.8%, and 0.97, respectively. The average coking rate was 0.0946 mg g_cat⁻¹ h⁻¹.     

Evaluation of Ni/Y2O3/Al2O3 catalysts for hydrogen production by autothermal reforming of methane

Ni/xY₂O₃–Al₂O₃ (x = 5, 10, 15, 20 wt%) catalysts were prepared by sequential impregnation synthesis. The catalytic performance for the autothermal reforming of methane was evaluated and compared with Ni/γ-Al₂O₃ catalyst. The physicochemical properties of catalysts were characterized by X-ray diffraction (XRD), Transmission electron microscope (TEM), X-Ray Photoelectron Spectrometer (XPS), Thermo Gravimetric Analyzer (TGA) and H₂-temperature programmed reduction techniques (TPR). The decrease of nickel particle size and the change of reducibility were found with Y modification. The CH₄ conversion increased with elevating levels of Y₂O₃ from 5% to 10%, then decreased with Y content from 10% to 20%. Ni/xY₂O₃–Al₂O₃ catalysts maintained high activity after 24 h on stream, while Ni/Al₂O₃ had a significant deactivation. The characterization of spent catalysts indicated that the addition of Y retarded Ni sintering and decreased the amount of coke.     

Evaluation of Pt–Ru–Ni and Pt–Sn–Ni catalysts as anodes in direct ethanol fuel cells

In this study, the electrooxidation of ethanol on carbon supported Pt–Ru–Ni and Pt–Sn–Ni catalysts is electrochemically studied through cyclic voltammetry at 50 °C in direct ethanol fuel cells. All electrocatalysts are prepared using the ethylene glycol-reduction process and are chemically characterized by energy-dispersive X-ray analysis (EDX). For fuel cell evaluation, electrodes are prepared by the transfer-decal method. Nickel addition to the anode improves DEFC performance. When Pt₇₅Ru₁₅Ni₁₀/C is used as an anode catalyst, the current density obtained in the fuel cell is greater than that of all other investigated catalysts. Tri-metallic catalytic mixtures have a higher performance relative to bi-metallic catalysts. These results are in agreement with CV results that display greater activity for PtRuNi at higher potentials.     

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.     

On the activity of bimetallic catalysts for ethanol steam reforming

The performance of CeO₂-supported Pt–Ni and Pt–Co catalysts in the low temperature-Ethanol Steam Reforming (ESR) reaction has been evaluated studying the effect of the preparation method (impregnation/coprecipitation) and parameters such as dilution ratio, temperature, water-to-ethanol feed ratio and Gas Hourly Space Velocity (GHSV). The results show that impregnated samples perform better. In particular, the Pt/Ni/CeO₂ catalyst starting from 350 °C leads to a products distribution very close to the equilibrium calculations, with a low CO content that is ideal for fuel cells devices. In addition, the Co-based catalysts appear attractive in terms of hydrogen yield and coking tendency.     

A comparative study of catalytic behaviors of Mn,Fe, Co,Ni, Cu and Zn–Based catalysts in steam reforming of methanol,acetic acid and acetone

This study investigated the distinct catalytic behaviors of mono Mn, Fe, Co, Ni, Cu and Zn catalysts in the reforming of the small organics including methanol, acetic acid and acetone. The results showed that Mn, Fe or Zn-based catalysts showed almost no activity for steam reforming of either methanol, acetic acid or acetone, due to their low capacity to break the chemical bonds of the organics or to activate steam. Co and Cu-based catalysts were generally active for steam reforming of methanol. Nevertheless, Co-based catalysts promoted methanol decomposition to form a substantial amount of CO. Alumina as a support remarkably influenced catalytic stability of the catalyst. The unsupported Cu catalyst showed a much lower stability than Cu/Al₂O₃. Nevertheless, the unsupported Ni was more stable than Ni/Al₂O₃ catalyst, due to its high resistivity towards coking. The unsupported Co, however, was prone to coking. The C/H ratios in the coke formed over the unsupported and alumina-supported Ni or Co catalysts were distinct, indicating the involvement of alumina in the coking process. In addition, Ni and Co catalysts behaved differently. Ni/Al₂O₃ showed a superior stability than Co/Al₂O₃ in steam reforming of acetone. The coke formed on Ni/Al₂O₃ was more aromatic than that over Co/Al₂O₃ catalysts while morphologies of coke (nanotubes over Ni/Al₂O₃ versus fibrous coke over Co/Al₂O₃) were also different.     

Ni and Co-based catalysts supported on ITQ-6 zeolite for hydrogen production by steam reforming of ethanol

Ni and Co catalysts supported on ITQ-6 zeolite have been synthesized and evaluated in the steam reforming of ethanol (SRE). Catalysts were also characterized by means of N₂ adsorption-desorption, XRD, H₂-TPR, and H₂-chemisorption. ITQ-6 containing Co (Co/ITQ-6) presented a higher conversion of ethanol and production of hydrogen than ITQ-6 containing Ni (Ni/ITQ-6). The lower size of the metallic cobalt particles shown in Co/ITQ-6 seems to be the major responsible of its higher catalytic performance. Regarding the reaction by-products (CO, CH₄, C₂H₄O and CO₂), Co/ITQ-6 showed the lowest selectivity at medium and high temperatures (773 and 873 K). At low reaction temperatures (673 K) the dehydrogenation reaction predominates in the Co/ITQ-6, what it is supported by the high concentration of acetaldehyde detected at this temperature. In the case of the Ni/ITQ-6 the main side reaction at 673 K seems to be the methanation reaction since large concentrations of methane are detected. Stability studies were also carried out showing lower deactivation of Co/ITQ-6 at large reaction times (24 h). Characterization of the exhausted catalysts after reaction showed the presence of coke in both catalysts. Nevertheless, Co/ITQ-6 presented the lowest coke deposition. In addition, Co/ITQ-6 exhibited the lowest metal sinterization, what could be also account for the lower deactivation exhibited by this sample. This fact could be related to the higher interaction between the cobalt metallic particles and the ITQ-6 support as the H₂-TPR studies demonstrate.     

The promotional effects of plasma treating on Ni/Y2Ti2O7 for steam reforming of methane (SRM): Elucidating the NiO-support interaction and the states of the surface oxygen anions

To explore the interaction between NiO and Y₂Ti₂O₇ support, and fabricate improved catalysts for SRM, several Ni/Y₂Ti₂O₇ catalysts have been prepared by an impregnation method with the assistance of dielectric barrier discharge (DBD) plasma treating in different atmospheres. It is found that both the reaction performance and anti-coking ability are improved for the catalysts in comparison with the untreated sample, following the sequence of Ni/Y₂Ti₂O₇–H₂P > Ni/Y₂Ti₂O₇-ArP > Ni/Y₂Ti₂O₇-AirP > Ni/Y₂Ti₂O₇. H₂-TPR and XPS results have demonstrated that plasma treatment effectively strengthens the interaction between NiO and Y₂Ti₂O₇ support, and Ni²⁺ cations preferentially interact solely with the Y³⁺ cations in the A site of Y₂Ti₂O₇. As a consequence, the agglomeration of the metallic Ni species during the reduction process can be impeded, thus obtaining catalysts possessing higher Ni dispersion. As evidenced by Raman, EPR and XPS results, superoxide O₂⁻ anions induced by the intrinsic 8a oxygen vacancies of Y₂Ti₂O₇ pyrochlore phase is the only kind of active surface oxygen sites, which might play a critical role for coking removing, and whose formation can be significantly facilitated by plasma treating. In conclusion, the improved active Ni surface area and the surface active superoxide O₂⁻ amount by DBD plasma treating are the major factors responsible for the enhanced reaction performance and coking resistance of the catalysts.     

Ni/Y2B2O7 (BTi,Sn, Zr and Ce) catalysts for methane steam reforming: On the effects of B site replacement

In this study, a series of Y₂B₂O₇ compounds with a fixed Yttrium cation A site but with different B (BTi, Sn, Zr and Ce) sites have been synthesized and used to support Ni for methane reforming for hydrogen production. By replacing the B site with Ti, Sn, Zr and Ce cations in sequence, the r_A/r_B ratios of the resulted Y₂B₂O₇ compounds become smaller. As a consequence, the crystalline structures of the compounds become less ordered with the transformation of the bulk phase from well-ordered pyrochlore (Y₂Ti₂O₇) to less ordered pyrochlore (Y₂Sn₂O₇) and subsequently to defective fluorite (Y₂Zr₂O₇ and Y₂Ce₂O₇). XPS results have revealed that on the surfaces of Ni/Y₂Ti₂O₇ and Ni/Y₂Ce₂O₇, higher O/(Y + B) atomic ratios can be achieved than on the other two catalysts, indicating the presence of more abundant oxygen species, which is beneficial to remove the carbon deposits. In comparison with Y₂Zr₂O₇ and Y₂Ce₂O₇, the supported Ni or Ni₃Sn₂ active sites have stronger interaction with Y₂Ti₂O₇ and Y₂Sn₂O₇ supports, which anchors the active sites tighter on the supports and suppresses its aggregation effectively, thus obtaining catalysts with larger active metallic surface areas and better thermal stability. As a result, the stability and coking resistance of the catalysts can be enhanced. For the reduced Ni/Y₂Sn₂O₇, Ni₃Sn₂ alloy has formed, which improves the coking resistance of the catalyst but degrades its activity significantly. On Ni/Y₂Ti₂O₇ catalyst, which possesses the largest amount of active surface oxygen species, the strongest Ni interaction with the support can also be obtained, therefore, it exhibits the highest activity, stability and strongest coking resistance among all of the catalysts.     

Electrochemical impedance studies on carbon supported PtRuNi and PtRu anode catalysts in acid medium for direct methanol fuel cell

The anodic Pt–Ru–Ni/C and the Pt–Ru/C catalysts for potential application in direct methanol fuel cell (DMFC) were prepared by chemical reduction method. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) measurements were carried out by using a glassy carbon working electrode covered with the catalyst powder in a solution of 0.5 mol L⁻¹ CH₃OH and 0.5 mol L⁻¹ H₂SO₄ at 25 °C. EIS information discloses that the methanol electrooxidation on the Pt–Ru–Ni/C catalyst at various potentials shows different impedance behaviors. The mechanism and the rate-determining step of methanol electrooxidation are changed with increasing potential. Its rate-determining steps are the methanol dehydrogenation and the oxidation reaction of adsorbed intermediate CO_ads and OH_ads in low (400–500 mV) and high (600–800 mV) potentials, respectively. The catalytic activity of the Pt–Ru–Ni/C catalyst is higher for methanol electrooxidation than that of the Pt–Ru/C catalyst. Its tolerance performance to CO formed as one of the intermediates of methanol dehydrogenation is also better than that of the Pt–Ru/C catalyst.     

Coke deactivation of Ni and Co catalysts in ethanol steam reforming at mild temperatures in a fluidized bed reactor

The deactivation by coke deposition of Ni and Co catalysts in the steam reforming of ethanol has been studied in a fluidized bed reactor under the following conditions: 500 and 700 °C; steam/ethanol molar ratio, 6; space time, 0.14 g_catalyst h/g_ethanol, partial pressure of ethanol in the feed, 0.11 bar, and time on stream up to 20 h. The decrease in activity depends mainly on the nature of the coke deposited on the catalysts, as well as on the physical–chemical properties (BET surface area, pore volume, metal surface area) of the catalysts. At 500 °C (suitable temperature for enhancing the WGS reaction, decreasing energy requirements and avoiding Ni sintering), the main cause of deactivation is the encapsulating coke fraction (monoatomic and polymeric carbon) that blocks metallic sites, whereas the fibrous coke fraction (filamentous carbon) coats catalyst particles and increases their size with time on stream with a low effect on deactivation, especially for catalysts with high surface area. The catalyst with 10 wt% Ni supported on SiO₂ strikes a suitable balance between reforming activity and stability, given that both the capability of Ni for dehydrogenation and C–C breakage and the porous structure of SiO₂ support enhance the formation of filamentous coke with low deactivation. This catalyst is suitable for use at 500 °C in a fluidized bed, in which the collision among particles causes the removal of the external filamentous coke, thus minimizing the pore blockage of the SiO₂. At 700 °C, the coke content in the catalyst is low, with the coke being of filamentous nature and with a highly graphitic structure.     

Hydrogen production from oxidative steam-reforming of n-propanol over Ni/Y2O3–ZrO2 catalysts

Oxidative steam reforming (OSR) of n-propanol was studied over new Ni catalysts (ca. 7% Ni wt/wt) supported on Y₂O₃–ZrO₂ oxides with different yttrium content (2–41 % Y₂O₃ wt/wt). Materials were characterized by X-ray diffraction, temperature-programmed reduction, X-ray photoelectron and Raman spectroscopy, scanning electron microscopy with energy dispersive X-ray analysis and high resolution transmission electron microscopy. Samples were used in calcined form and tested in the temperature range 673–773 K using a reactant feed of n-propanol/water/O₂ at a molar ratio 1/9/0.5. Hydrogen production is related with the support composition and Ni dispersion.     

Effect of CaO–ZrO2 addition to Ni supported on γ-Al2O3 by sequential impregnation in steam methane reforming

Ni catalysts supported on (CaO–ZrO₂)-modified γ-Al₂O₃ were prepared by sequential impregnation. The effects of varied CaO to ZrO₂ mole ratios at 0, 0.20, 0.35, 0.45, and 0.55 on the activity and stability of the modified Ni catalysts were studied. As a result of using CaO–ZrO₂ as a promoter, each catalyst contained CaO–ZrO₂ at only 5%. γ-Al₂O₃ used as support was modified by CaO–ZrO₂ before the deposition of nickel oxide. The addition of CaO–ZrO₂ at an optimum ratio was expected to improve the stability of Ni catalysts due to the decrease of carbon formation resulting from carbon gasification. All the fresh catalysts were characterized by ICP, XRD, BET surface area, TGA in H₂, and TPR before catalytic testing in steam methane reforming at 600 °C. The spent catalysts were examined by TEM and TGA to observe the catalysts deactivation. The identification of CaO–ZrO₂ phases indicated that CaO and ZrO₂ reacted with each other to be monoclinic solid solution ZrO₂, CaZr₄O₉, CaZrO₃, and CaO corresponding to the phase diagram of CaO–ZrO₂. The existence of CaZrO₃ for 0.55 mol ratio of CaO/ZrO₂ enhanced activity in steam methane reforming because oxygen vacancies in CaZrO₃ greatly preferred the water adsorption creating the favorable conditions for carbon gasification and, then, water gas shift. The prominence and continued existence of these two reactions on the Ni catalysts leads to the particular increase of H₂ yield. Moreover, the increasing amount of CaZrO₃ in the Ni catalysts significantly improved carbon gasification. However, the Ni catalysts with CaZrO₃ showed whisker carbon after catalytic testing; this carbon specie has not been tolerated in steam methane reforming. Therefore, these results significantly differed from the hypothesis.