CO2 methanation over Ni and Rh based catalysts: Process optimization at moderate temperature

H₂ was produced from aluminum/water reaction and reacted with CO₂ over Ni and Rh based catalysts to optimize the process conditions for CO₂ methanation at moderate temperature. Monometallic catalysts were prepared by incorporating Ni and Rh using nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O) and rhodium(III) chloride trihydrate (RhCl₃·3H₂O)as a precursor chemical. The preliminary study of the catalysts revealed higher activity and CH₄ selectivity for Rh based catalyst compared to that of Ni based catalyst. Further, Rh based catalyst was investigated using response surface methodology (RSM) involving central composite design. The quadratic model was employed to correlate the effects of variable parameters including methanation temperature, %humidity, and catalyst weight with the %CO₂ conversion, %CH₄ selectivity, and CH₄ production capacity. Analysis of variance revealed that methanation temperature and humidity play an important role in CO₂ methanation. Higher response values of CO₂ conversion (54.4%), CH₄ selectivity (73.5%) and CH₄ production capacity (8.4 μmol g^?1 min^?1) were noted at optimum conditions of 206.7°C of methanation temperature, 12.5% humidity and 100 mg of the catalyst. The results demonstrated the ability of Rh catalyst supported on palm shell activated carbon (PSAC) for CO₂ methanation at low temperature and atmospheric pressure.     

Enhanced activity of CO2 methanation over mesoporous nanocrystalline Ni–Al2O3 catalysts prepared by ultrasound-assisted co-precipitation method

The ultrasound-assisted co-precipitation method was employed for the synthesis of the Ni–Al₂O₃ catalysts with different metal loadings for the CO₂ methanation reaction. This study indicated that increasing the Ni loading up to 25 wt.% enhanced the surface area, decreased the crystallinity and improved the reducibility of the catalysts, while further raise in Ni loading adversely influenced the surface area. Improvements in catalytic performance were obtained with the raise in Ni content because of enhancing the BET area. The results confirmed that the 25Ni–Al₂O₃ catalyst with the highest BET area (188 m² g^?1) and dispersion of Ni has the highest catalytic activity in CO₂ methanation and reached to 74% CO₂ conversion and 99% CH₄ selectivity at 350 °C. In addition, this catalyst exhibited a great stability after 10 h time-on-stream.     

Solid-state synthesis method for the preparation of cobalt doped Ni–Al2O3 mesoporous catalysts for CO2 methanation

In this study, a simple solid-state synthesis method was employed for the preparation of the Ni–Co–Al₂O₃ catalysts with various Co loadings, and the prepared catalysts were used in CO₂ methanation reaction. The results demonstrated that the incorporation of cobalt in nickel-based catalysts enhanced the activity of the catalyst. The results showed that the 15 wt%Ni-12.5 wt%Co–Al₂O₃ sample with a specific surface area of 129.96 m²/g possessed the highest catalytic performance in CO₂ methanation (76.2% CO₂ conversion and 96.39% CH₄ selectivity at 400 °C) and this catalyst presented high stability over 10 h time-on-stream. Also, CO methanation was investigated and the results showed a complete CO conversion at 300 °C.     

Methanation of carbon dioxide over Ni/CeO2 catalysts: Effects of support CeO2 structure

The CeO₂, which were prepared by hard-template method, soft-template method, and precipitation method, were used as support to prepare Ni/CeO₂ catalysts (named as NCT, NCS, and NCP catalysts, respectively). The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer–Emmett–Teller (BET). Hydrogen temperature-programmed reduction (H₂-TPR) was also used to study the reducibility of the support nickel precursors. Moreover, CO₂ catalytic hydrogenation methanation was used to investigate the catalytic properties of the prepared NCT, NCS, and NCP catalysts. H₂-TPR and XRD results showed that the NiO can be reduced by H₂ to produce metal Ni species, and the surface oxygen species existing on the surface of the support CeO₂ can also be reduced by H₂ to form surface oxygen vacancies. Low-angle XRD, TEM, and BET results indicated that the NCT and NCS catalysts had developed mesoporous structure and high specific surface area of 104.7 m² g^?1 and 53.6 m² g^?1, respectively. The NCT catalyst had the highest CO₂ methanation activity among the studied NCT, NCS, and NCP catalysts. The CO₂ conversion and CH₄ selectivity of the NCT catalyst can reach 91.1% and 100% at 360 °C and atmospheric pressure. The NCP catalyst, which had low specific surface area and low porosity, performed less CO₂ conversion and higher CH₄ selectivity than the NCT and NCS catalysts till 400 °C.     

Combustion-impregnation preparation of Ni/SiO2 catalyst with improved low-temperature activity for CO2 methanation

Exploiting Ni-based catalysts with excellent low-temperature activity is significant for CO₂ methanation, which is a promising route to CO₂ utilization. In this work, a facile combustion-impregnation method was developed to prepare the SiO₂ supported Ni catalysts. Small Ni particles (around 6 nm) and massive Ni–SiO₂ interface could be obtained due to the “combustion” process. The H₂-temperature programmed desorption (H₂-TPD) revealed the existence of Ni–SiO₂ interface and confirmed the high Ni dispersion obtained by this method, which were vital for the activation of reactant. Moreover, more medium basic sites which were beneficial for the CO₂ activation could also be created. In comparison with the reference Ni/SiO₂ catalyst prepared by the conventional impregnation method, much higher CO₂ conversion (66.9%) and more superior selectivity to CH₄ (94.1%) were achieved with the Ni/SiO₂-Gly catalyst at 350 °C. Additionally, it was also found that glucose, citric acid and glycine were all effective fuels for this combustion-impregnation method, and the as-prepared catalysts all exhibited greatly improved low-temperature activity. Therefore, this work represents an important step toward developing Ni-based catalysts for CO₂ methanation by a promising wide-used method.     

CO2 methanation in the presence of methane: Catalysts design and effect of methane concentration in the reaction mixture

The work in this paper evidences the viability of producing synthetic natural gas (SNG) via the methanation reaction tackling two fundamental challenges on methanation catalysis (i) the development of advanced catalysts able to achieve high CO₂ conversion and high methane yields and (ii) the unexplored effect of residual methane on the methanation stream. Both challenges have been successfully addressed using Ni/CeO₂-ZrO₂ catalysts promoted with Mn and Co. Mn does not seem to be a good promoter while Co prevents carbon deposition and secondary reactions. In fact, our Co-doped sample reached high levels of CO₂ conversion and CH₄ selectivity, especially at low reaction temperatures. In addition, this catalyst exhibits excellent catalytic behaviour when methane is introduced into the gas mixture, indicating its feasibility for further study to be conducted in realistic flue gases environments and methanation units with recycling loops. Furthermore, when methane is introduced in the reactant mixture, the Ni-Co/CeO₂-ZrO₂ sample is very stable maintaining high levels of conversion and selectivity. Overall our Co-doped catalyst can deliver high purity synthetic natural gas for long-term runs, promising results for gas-phase CO₂ conversion units.     

Alumina-supported cobalt catalysts in the hydrogenation of CO2 at atmospheric pressure

20 wt.% cobalt catalysts supported on pure and 5 wt.% silica-containing alumina have been prepared and characterized by X-Ray Diffraction, IR and DR-UV-vis-NIR spectroscopies and Field-Emission Scanning Electron Microscopy (FE-SEM). The presence of a cobalt-containing surface spinel phase Co_3-xAl_xO₄ and, for the silica-containing sample, of a segregated Co₃O₄ phase is evident. These catalysts have been tested in CO₂ hydrogenation at atmospheric pressure in steady state conditions in the temperature range 523–773 K. Both catalysts are active in CO₂ hydrogenation to methane (methanation) and to CO (reverse Water Gas Shift, rWGS). CO₂ hydrogenation activity is higher on freshly pre-reduced silica-free Co/Al₂O₃, while selectivity to methane is slightly higher on the silica-containing sample. Spent catalysts contain clustered or amorphous cobalt metal centers as active sites for methanation. The silica-containing catalyst shows slow deactivation in CO₂ hydrogenation upon 13 h experiments, with quite stable or even slightly increasing rWGS activity and decreasing CH₄ selectivity. This confirms previous data suggesting that, over cobalt catalysts, sites for methanation are metal centers prone to deactivation by carbon deposition. However, in contrast with what happens with unsupported and silica-supported cobalt catalysts, where deactivation is very fast, over these alumina-based catalysts carbon deposition and deactivation occur much more slowly. Sites for rWGS are unreduced cobalt centers which do not undergo such a deactivation phenomenon.     

Thermal management of CO2 methanation with axial staging of active metal concentration in Ni-YSZ tubular catalysts

CO₂ methanation has attracted considerable interests as a promising approach to productively utilizing CO₂ and reducing emissions to realize a low-carbon society. One major difficulty with packed bed reactors for catalyzed CO₂ methanation is maintaining an optimal reactor temperature distribution. Although a high temperature increases the catalytic activity, it also leads to the formation of an inlet hotspot, which causes thermal runaway, unfavorable equilibrium products, and catalyst degradation. To address this, in this study, we proposed an approach to manage the temperature profile in CO₂ methanation reactors by increasing catalytic activity along the reactor length using different Ni composition catalysts (gradient-distributed Ni-YSZ catalyst). Ni-based tubular catalysts with different Ni compositions were prepared and stacked in order of ascending Ni content from the inlet to the outlet. The effect of gradient Ni compositions on the temperature profile was investigated based on both numerical simulations and experimental observations. The gradient-distributed Ni catalyst could successfully prevent hotspot formation at the inlet of the reactor compared to the highly active uniform catalysts. The use of the catalyst caused a small difference in the reactor temperature (of ~70 °C) and afforded a high CH₄ yield (~90%). The proposed approach using gradient-distributed catalysts could be a potential method to manage CO₂ methanation reactor temperature and to achieve high CO₂ conversion in compact reactors.     

La-promoted Ni/Mg-Al catalysts with highly enhanced low-temperature CO2 methanation performance

In this paper, we investigated the effect of adding lanthanum on the structure and low-temperature activity of the Ni/Mg-Al catalyst for CO₂ methanation. A series of La-doped Ni/Mg-Al catalysts with different La loadings were synthesized by urea hydrolysis method. The results showed that La-promoted NiLax (x = 2, 5 and 8 wt%) catalysts exhibited higher low-temperature activity than the Ni catalyst without La added. In particular, the NiLa5 catalyst performed the best, getting as high as 61% CO₂ conversion and nearly 100% CH₄ selectivity at 250 °C, 0.1 MPa, and a WHSV of 45,000 mL g^?1 h^?1. Characterization results revealed that La effectively increased Ni dispersion and decreased Ni particle size. In addition, La could significantly increase the amount of moderate basic sites, which contributed to enhanced CO₂ adsorption capacity. Compared with coprecipitation method, urea hydrolysis method was proved to be a more efficient approach for the Ni-based catalyst preparation, getting the Ni-based catalyst with higher Ni dispersion, larger CO₂ adsorption capacity and thereby better catalytic performance.     

Low-temperature catalytic conversion of greenhouse gases (CO2 and CH4) to syngas over ceria-magnesia mixed oxide supported nickel catalysts

Running dry reforming of methane (DRM) reaction at low-temperature is highly regarded to increase thermal efficiency. However, the process requires a robust catalyst that has a strong ability to activate both CH₄ and CO₂ as well as strong resistance against deactivation at the reaction conditions. Thus, this paper examines the prospect of DRM reaction at low temperature (400–600 °C) over CeO₂–MgO supported Nickel (Ni/CeO₂–MgO) catalysts. The catalysts were synthesized and characterized by XRD, N₂ adsorption/desorption, FE-SEM, H₂-TPR, and TPD-CO₂ methods. The results revealed that Ni/CeO₂–MgO catalysts possess suitable BET specific surface, pore volume, reducibility and basic sites, typical of heterogeneous catalysts required for DRM reaction. Remarkably, the activity of the catalysts at lower temperature reaction indicates the workability of the catalysts to activate both CH₄ and CO₂ at 400 °C. Increasing Ni loading and reaction temperature has gradually increased CH₄ conversion. 20 wt% Ni/CeO₂–MgO catalyst, CH₄ conversion reached 17% at 400 °C while at 900 °C it was 97.6% with considerable stability during the time on stream. Whereas, CO₂ conversions were 18.4% and 98.9% at 400 °C and 900 °C, respectively. Additionally, a higher CO₂ conversion was obtained over the catalysts with 15 wt% Ni content when the temperature was higher than 600 °C. This is because of the balance between a high number of Ni active sites and high basicity. The characterization of the used catalyst by TGA, FE-SEM and Raman Spectroscopy confirmed the presence of amorphous carbon at lower temperature reaction and carbon nanotubes at higher temperature.     

Enhanced CO2 hydrogenation to light hydrocarbons on Ni-based catalyst by DBD plasma

The high thermal stability of CO₂ makes its conversion low in conventional thermal catalysis. Comparatively, non-equilibrium plasma technique provides an efficient way for CO₂ hydrogenation under mild reaction conditions. Introducing effective catalysts to the dielectric barrier discharge (DBD) plasma reactor may further improve CO₂ hydrogenation performance. In this way, the interaction between plasma and catalysts is important to contribute CO₂ hydrogenation performance. Considering Ni-based catalyst is active for CO₂ hydrogenation, we used three different kinds of carrier materials including CeO₂, γ-Al₂O₃ and ZSM-5 as supports to prepare nickel-based catalysts by incipient impregnation in this paper. The supported Ni catalysts were tested for the plasma-induced CO₂ hydrogenation to CH₄ and C₂₊ hydrocarbons in the DBD-plasma reactor. It was found that the 15Ni/CeO₂ catalyst achieved the best CO₂ conversion of 85.7% and nearly 100% CH₄ selectivity at 300 °C due to its high reducibility and CO₂ chemisorption capacity. In addition, a significant synergistic effect was found between DBD plasma and catalyst. The performance of plasma-catalysis was considerably better than that of thermal catalysis plus pure plasma reaction, and the synergistic effects were enhanced with increase of reaction temperature. Moreover, the mechanism of the synergistic effect was proposed by analyzing the optical emission spectroscopy (OES) of DBD plasma, which provides a theoretical basis for further optimizing and application of plasma-catalysis for CO₂ hydrogenation reaction.     

Solution plasma-assisted preparation of highly dispersed NiMnAl-LDO catalyst to enhance low-temperature activity of CO2 methanation

In this work, the solution plasma-assisted method was used to prepare NiMnAl-LDO (layered double oxides) catalysts with different treatment times, which were used for the CO₂ methanation reaction. Solution plasma treatment can enhance the dispersibility of the catalyst, create oxygen defects and improve the chemical adsorption capacity of the catalyst. The results show that the low-temperature activity of the catalyst has been improved after the solution plasma treatment. We demonstrate that the NiMnAl-LDO-P(20) catalyst with high dispersion has the highest catalytic activity in CO₂ methanation (81.3% CO₂ conversion and 96.7% CH₄ selectivity at 200 °C). Even though working for 70 h, the catalyst is still highly stable. This work provides a great promise for improving the low-temperature activity of Ni-based catalysts.     

Vanadium promoted Ni(Mg,Al)O hydrotalcite-derived catalysts for CO2 methanation

A series of V-promoted hydrotalcite-derived nickel catalysts (1.0, 2.0, and 4.0 wt%) were tested in CO₂ methanation. Ni–I–V2.0 with 2.0 wt% vanadium loading showed the highest catalytic activity, achieving 74.7% of CO₂ conversion and 100% of CH₄ selectivity at 300 °C. XRD and XANES analyses showed that the smallest Ni⁰ particles in Ni–I–V2.0 were consistent with the improved textural features observed for this catalyst. Moreover, CO₂-TPD revealed the highest sum of weak and medium basic sites in Ni–I–V2.0 that can positively influence catalytic behavior. For the studied catalysts, a clear correlation was demonstrated between the catalytic activity and specific surface area, as well as the basic properties.     

Mesoporous zirconia-modified clays supported nickel catalysts for CO and CO2 methanation

The Ni catalysts supported on a new structure with zirconia nanoparticles highly dispersed on the partly damaged clay layers has been prepared by the incipient wetness impregnation method and the new structure of the support has been prepared in one pot by the hydrothermal treatment of the mixture of the clay suspension and the ZrO(NO₃)₂ solution. The catalytic performances for the CO and CO₂ methanation on the catalysts have been investigated at a temperature range from 300 °C to 500 °C at atmospheric pressure. The catalysts and supports have been characterized by X-ray diffraction (XRD), transmittance electron microscopy (TEM), H₂ temperature-programmed reduction (H₂-TPR), nitrogen adsorption–desorption, and thermogravimetry and differential thermal analysis (TG-DTA). It is found that the zirconia-modified clays have the typical bimodal pore size distribution. Most of the pores with the sizes smaller than 10 nm are resulted from the zirconia pillared clays and the mesopores with the sizes larger than 10 nm and the macropores with the sizes larger than 50 nm are resulted from the partly damaged clay layers. The bimodal pore structure is beneficial to the dispersion of Ni on the layers of the zirconia-modified clays and the increase in Ni loading. The zirconia nanoparticles are highly dispersed on the partly damaged clay layers. Nickel oxide in cubic phase is the only Ni species that can be detected by XRD. The nickel oxide nanoparticles with the sizes of 12 nanometers or more are well dispersed on the zirconia-modified clay layers, which are observed to be buried in the stack layers of zirconia. The presence of nickel oxide in six different forms could be perceived on the new structure. Five of them except the Ni species that forms the spinel phase with Al in clays can be reduced to the active Ni species for the CO and CO₂ methanation. But the activity of the Ni species is different, which is associated with the chemical environment at which the Ni species is located. The catalyst with the higher zirconia content, which also has the larger specific surface area and pore volume, exhibits the better catalytic performance for the CO or CO₂ methanation. Zirconia in the catalyst is responsible for the dispersion of the Ni species, and it prevents the metallic Ni nanoparticles from sintering during the process of the reaction. In addition, it is also responsible for the reduction of the inactive carbon deposition. The catalyst with 15 wt.% zirconia content has the highest CO conversion of about 100% and the highest methane selectivity of about 93% at 450 °C for CO methanation, and the catalyst with 20% zirconia content has the CO₂ conversion of about 80% and the highest methane selectivity of about 99% for CO₂ methanation at 350 °C. The catalyst with 15 wt.% zirconia possesses promising stability and no distinct deactivation could be perceived after reaction for 40 h. This new catalyst has great potential to be used in the conversion of the blast furnace gas (BFG) and the coke oven gas (COG) to methane.     

CO2 methanation over nanocrystalline Ni catalysts supported on mechanochemically synthesized Cr2O3-M (M=Fe,Co, La,and Mn) carriers

In the present study, a series of Cr₂O₃ powders modified by different promoters such as Fe, Co, La, and Mn were synthesized using a facile and solvent-free mechanochemical method and the prepared powders were used as a catalyst carrier for the preparation of 20 wt%Ni catalysts in CO₂ methanation. The results indicated that among all catalysts, the nickel catalyst supported on the Mn-promoted Cr₂O₃ exhibited the best catalytic performance. The results showed that there was an optimum for the Mn content and the increment in Mn content up to 15 wt% improved the catalytic performance due to its positive influence on increasing nickel dispersion and catalyst reducibility. The 20 wt%Ni/15 wt%Mn–Cr₂O₃ catalyst possessed a CO₂ conversion of 72.12% and CH₄ selectivity of 100% at 350 °C (H₂/CO₂ = 3 M ratio, GHSV = 18,000 ml/g_cat.h) with high stability during 12 h on stream. The obtained results showed that the increment in H₂/CO₂ molar, and the decrement in GHSV value and calcination temperature improved the catalytic performance.     

Highly stable Ni-based catalysts derived from LDHs supported on zeolite for CO2 methanation

CO₂ methanation can effectively reduce the concentration of CO₂ in the air and decrease environmental pollution. Therefore, it is essential to synthesize catalysts with high carbon deposition resistance and stability. Herein, the highly stabilized Ni-based catalysts derived from hydrotalcites are prepared by the self-sacrificial template method and used for CO₂ methanation. The prepared Ni-based catalysts maintain the morphology of the hydrotalcites precursors and the Ni particles are embedded in the AlO_x substrate. The catalyst show high performance at 350 °C, 0.1 MPa and a high space velocity of 30,000 mL g⁻¹ h⁻¹, with the conversion rate of CO₂ and selectivity of CH₄ reaching 87.5% and 100%, respectively. More importantly, the activity of catalyst does not decrease after continuous reaction for 200 h at 350 °C with different space velocities (30,000 and 60,000 mL g⁻¹ h⁻¹) owing to the confinement of the AlO_x substrate, which suppress the undesirable agglomeration and sintering of the Ni particles. This unique mosaic structure has certain reference significance for studying materials with excellent stability at high temperatures.     

Which is the better catalyst for CO2 methanation – Nanotubular or supported Ni-phyllosilicate?

In order to investigate effects of morphology and crystalline phase of different Ni-phyllosilicate catalysts on the catalytic performance for CO₂ methanation, nanotubular Ni-phyllosilicate and MCM-41 supported Ni-phyllosilicate were synthesized through hydrothermal reaction of sodium silicate or MCM-41 with nickel nitrate. On one hand, nanosheets attributing to 2:1 type nickel phyllosilicate (Ni₃Si₄O₁₀(OH)₂·5H₂O) were uniformly grown on the surface of MCM-41 spheres to form the MCM-41 supported Ni-phyllosilicate (Ni/M). On the other hand, 1:1 type Ni-phyllosilicate with nanotubular morphology (Ni/N) was synthesized through the reaction of Na₂SiO₃ and nickel nitrate. After a series of tests and characterizations, it was found that Ni/N exhibited low thermal stability and poor anti-sintering property, leading to poor catalytic activity for CO₂ methanation. On the contrary, Ni/M was very stable, which obtained unchanged morphology and fine Ni particles after 750^oC-reduction, resulting in high catalytic activity and long-term stability for CO₂ methanation. In all, morphology and crystalline phase of Ni-phyllosilicate obviously affected catalytic performance, and the supported Ni-phyllosilicate catalyst was much better than the nanotubular Ni-phyllosilicate for CO₂ methanation in this work.     

Enhanced dry reforming of methane over mesostructured fibrous Ni/MFI zeolite: Influence of preparation methods

Dry reforming of methane is acknowledged to be an environmentally benign route for conversion of CO₂ and CH₄ into syngas (CO and H₂). Herein, unique mesostructured fibrous MFI support was synthesized by microemulsion method, and Ni incorporation via double solvent, physical mixing and wetness impregnation methods. Results revealed wetness impregnation catalyst had the highest activity and stability. Activation energy of reactants showed a reliance on acidity, where moderate acidity impeded deactivation by CH₄ cracking. Furthermore, degree of catalyst deactivation was negligible compared to what is attainable on conventional zeolite catalysts. Thus, fibrous morphology, microscopic dispersion and moderate acidity played a positive role in boosting reactants accessibility to active Ni sites which results in preservation of activity under the harsh conditions of DRM process.     

Hydrogen production from aqueous phase reforming of glycerol over attapulgite-supported nickel catalysts: Effect of acid/base treatment and Fe additive

In this paper, a series of nickel-based catalysts supported on modified attapulgite (ATP) by acid (citric acid and EDTA) and base (NaOH) were prepared and applied to the aqueous phase reforming of glycerol (APRG). The modified ATP (MA) and as-prepared catalysts were detected using N₂ adsorption-desorption, ICP-OES, XRD, FT-IR, SEM-EDS, HRTEM, XPS, H₂-TPR, NH₃-TPD. The results manifested that the acid/base treatment of ATP significantly increased the surface area and pore volume, enhanced the metal-support interaction (MSI) and decreased the Ni particle size, resulting in the better glycerol conversion and H₂ selectivity, especially for Ni/MA-E catalyst, where the ATP was pretreated using EDTA. In addition, the bimetallic NiFe/MA-E catalyst exhibited the highest conversion of glycerol to gas product (54.4%) and H₂ selectivity (84.6%) at very low temperature (280 °C). These results were attributed to the strongest the interplay of active metal with support by the formation of Ni–Fe alloy, resulting in the highest active metal dispersion, smallest metal particle size, lowest the reducibility of active metal and most surface Ni⁰ content. According to the characterizations of spent catalysts, it demonstrated that monometallic Ni catalysts presented obvious sintering of Ni metal particle and larger accumulation of carbon deposition, which led to the deactivation of the catalyst. While NiFe/MA-E catalyst showed less particle agglomeration and coke formation attributed to the lower content of surface acid site. Apart from that, another cause of catalyst deactivation might be the destruction of ATP skeleton during APRG.     

Unveiling the promotion effect of Zr species on SBA-15 supported nickel catalysts for CO2 methanation

Introducing promoters on Ni-based catalysts for CO₂ methanation have been proved to be positive for enhancing their performance. And the correlation of the promotion mechanism and the reaction pathway is significant for designing efficient catalysts. In this contribution, series of Zr species promoted SBA-15 supported Ni catalysts were prepared by citric acid complexation method under a range of Zr/Ni atomic ratios from 0 to 2.5. In situ and ex situ characterizations were carried out. It was found that the addition of citric acid was conductive to improve CH₄ selectivity due to the higher concentrations of Ni⁰ confined in SBA-15, harvesting sufficient H atoms for CH₄ formation following formate pathway via a formyl intermediate. Furthermore, a coverage layer of Zr species was found on the support at Zr/Ni = 1.7, which interacted with the Ni particles, providing higher concentrations of medium basic sites for CO₂ activation. Accordingly, the optimum catalytic performance was obtained on ZrNi-1.7(CI), achieving CO₂ conversion as high as 78.1% and nearly 100% CH₄ selectivity at 400 °C, following the formate hydrogenation pathway. In addition, the ZrNi-1.7(CI) showed good stability owing to the confinement effect of SBA-15 and the Ni–Zr interaction, no carbon deposits were detected after 50 h test.