The Impact of Ce-Zr Addition on Nickel Dispersion and Catalytic Behavior for CO 2 Methanation of Ni / AC Catalyst at Low Temperature

The CO2 methanation was studied over 7wt.% nickel supported on Ce0.2Zr0.8O2/AC to evaluate the correlation of the structural properties with catalytic performance. The catalysts were investigated in more detail by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), and scanning electron microscopy (SEM). A sample of 7 wt.% nickel loading supported on activated carbon (AC) was also prepared for comparison. The results demonstrated that the ceria-zirconia solid solution phase could disperse and stabilize the nickel species more effectively and resulted in stronger interaction with nickel than the parent activated carbon phase. Therefore, 7% Ni/Ce0.2Zr0.8O2/AC catalyst exhibited higher activity for CO2 reduction than 7% Ni//AC. It can attain 85% CO2 conversion at 350 C and have a CH4 selectivity of 100% at a pressure as low as 1 atm. The high activity of prepared catalysts is attributed to the good interaction between Ni and Ce0.2Zr0.8O2 and the high CO2 adsorption capacity of the activated carbon as well.


Introduction
Increasing emissions of carbon dioxide arising from the widespread production of energy from fossil fuels is a critical matter regarding greenhouse gases effect and, thus, global warming [1,2].Technologies including possible reduction or conversion of CO 2 give valuable advantages for protecting the environment by recycling CO 2 effectively based on the catalytic methanation [3][4][5].Conversion of carbon oxides into methane is a exothermic reaction with ΔH ∘ = −165 kJ/mol.The exothermic character of the methanation process causes problems with respect to an exact control of the reaction temperature, which can result in a further increased conversion of CO 2 [6].Therefore, the development of catalysts for methanation of carbon dioxide is the key factor.Recently, results of Beuls et al. [7] and Jacquemin et al. [8] give evidences that at low temperature (<200 ∘ C) and atmospheric pressure the reaction takes place with very high selectivity.
Firstly, adding catalyst promoters, Trovarelli et al. [36,37], who compared the catalytic activity of several Rh-based catalysts using different types of supports, CeO 2 , SiO 2 , Ta 2 O 2 , (MD), and a climbing image nudged elastic band (CI-NEB) method.The results obtained indicate that CO 2 is easily adsorbed by Ni/AC.Usually, catalytic reaction properties can be affected by the catalyst composition and structure (e.g., specific surface area, pore size distribution, pore size, and structure).As is generally known, the support with high surface area will make the dispersion of active sites more easily and consequently a higher active surface area is generated.Highly dispersed supported nickel catalysts have been widely used in the hydrogenation of CO 2 to methane.Activated carbon, which is characterized by large specific surface areas (>1000 m 2 g −1 ) and developed pore structures, has exhibited good catalytic properties, thus making it of great interest to researchers in the field of catalysis.The nickel supported on activated carbon used for CO 2 catalytic hydrogenation had not been reported to date; we believe that activated carbon is a good support in modifying the surface properties to promote the nickel catalyst activity for hydrogenation of CO 2 .
In this article, the Ni/AC and Ni/Ce 0.2 Zr 0.8 O 2 /AC catalysts with 7 wt.%nickel loadings were prepared by the incipient wetness impregnation.In these catalysts, nickel species are considered as active sites supported on Tra Bac activated carbon (AC) or on Ce 0.2 Zr 0.8 O 2 /AC (mixed oxides Ce 0.2 Zr 0.8 O 2 deposited on AC).The catalysts and the supports were characterized by XRD, SEM, TEM, H2-TPR, and nitrogen adsorption-desorption.The activity and the CH 4 selectivity of the catalyst samples for the CO 2 methanation were also performed by a continuous flowing microreactor apparatus.Ce 0.2 Zr 0.8 O 2 mixed oxide was chosen because it promoted the dispersion of the nickel species on the supports and prevented the nickel species from sintering, leading to the high activity and the good stability.Activated carbon can act as a storage source of both H 2 and CO 2 and it helps in making the dispersion of nickel on the surface much easier.The highly dispersed nickel species are easily reduced and they are responsible for the high catalytic performance and for reducing the inactive carbon deposition.The goals of this study are to report the effects of CeO 2 -ZrO 2 promoter and of the pore structure of activated carbon on the dispersion of nickel species, as well as the catalytic performances for CO 2 methanation.The possible reasons for the effect of Ce 0.2 Zr 0.8 O 2 promoter on the catalytic activity of the Ni/AC catalyst were given.

Preparation of Ni Catalyst with Activated
Carbon as the Support.The Ni/AC was prepared by incipient wetness impregnation method at a nickel loading of 7 wt%.Typically, 1.74 g nickel nitrate hexahydrate, Ni(NO 3 ) 2 ⋅6H 2 O (99.0%, Merck), was dissolved in 30 mL distilled water.Then 5 g activated carbon support (coconut shell activated carbon was provided by Tra Bac factory, Vietnam) that was previously washed, crushed, and sieved to a size of 0.65-1 mm was added.The samples, subsequently, were dried in an oven at 60 ∘ C for 10 hours and continuously at 100 ∘ C for another 5 hours.Finally, the samples were calcined in N 2 environment at 400 ∘ C for 4 hours and then stored for further characterizations.The catalyst samples were denoted as 7 Ni/AC for weight percentage of 7% Ni.Nickel (the active phase, with the loading of 7 wt%) was deposited on the Ce 0.2 Zr 0.8 O 2 /AC samples by wet impregnation.Suitable amount (1.74 g) of Ni(NO 3 ) 2 ⋅6H 2 O (99.0 wt%, Merck) was dissolved in 30 mL distilled water; then the Ce 0.2 Zr 0.8 O 2 /AC support was immersed in the prepared solution for 5 min.The wet pellets were dried until becoming completely dry.This procedure was repeated until all the solution ran out.Finally, the impregnated samples were heated at a heating rate of 3 ∘ C/min till 200 ∘ C and maintained at 200 ∘ C for 4 h.The catalyst sample was then symbolized as 7 Ni/CeZrAC.

Characterization of Catalysts. X-ray powder diffraction
(XRD) patterns of the samples were obtained in a X-ray diffractometer (D8 Advance-Bruker) using Cu K radiation with a wavelength of 0.154 nm from 10 ∘ to 70 ∘ with a step size of 0.03 ∘ .The data were compared to reference data from JCPDS or ICDD.The particle size calculations were performed using the Scherrer equation.
Brunauer-Emmett-Teller (BET) specific surface areas, average pore diameter, and pore volume of the samples were determined by N 2 adsorption-desorption isotherm at 77 K using the BET (Brunauer-Emmett-Teller) method in a Micromeritics Tristar 3000 instrument.Before each measurement, the sample was degassed at 523 K for 4 hours.
The scanning electron microscopy (SEM) studies of the catalysts were performed on a scanning electron microscope (Hitachi S-4800) apparatus with an accelerating voltage of 10.0 kV.The samples were placed onto a metallic support and covered with a thin platinum film.
Transmission electron microscopy (TEM) studies were performed on a JEOL JEM-2000FX II instrument operated at 80.0 kV.All samples were suspended in ethanol by ultrasonication.The suspension was deposited on a copper grid with carbon film for TEM measurements.
Temperature-programmed reduction (TPR) measurements were carried out with a Micromeritics AutoChem 2920 instrument in a quartz U tube microreactor.Prior to the reduction the sample (app.40 mg) was purged with Ar (50 mL min −1 ) for 1 hour at 423 K to remove physically adsorbed water and then cooled down to room temperature.Afterwards, the sample is reduced in the flow of 10 vol% H 2 /Ar (50 mL min −1 ) at a heating rate of 10 K min −1 up to 973 K.The consumption of hydrogen was detected with a thermal conductivity detector (TCD) during the TPR procedure.

Evaluation of Catalysts.
The gas phase hydrogenation of CO 2 to methane was carried out in a continuous-flow fixedbed quartz reactor with an internal diameter of 1.5 mm under normal atmospheric pressure.A thermocouple was inserted into the catalyst bed to measure the reaction temperature.Typically for each run about 0.3 grams of catalyst pellets (similar size of 40-60 mesh) was loaded into a quartz reactor and reduced in situ under continuous flow of pure H 2 at the rate of 30 mL min −1 .The reduction temperature was programmed to increase from room temperature to 600 ∘ C and maintained at 600 ∘ C for 4 h.After reduction, the temperature was decreased to 100 ∘ C under the same hydrogenation flow and the catalyst was subsequently exposed to the feed gases CO 2 /H 2 /He with a molar ratio of CO 2 : H 2 : He = 1 : 4 : 5 at a gas hourly space velocity (GHSV) of 4000 mL⋅ g −1 cat ⋅h −1 under atmospheric pressure.Catalytic activity was measured at 100, 200, 250, 300, 350, 400, and 450 ∘ C. At each temperature, after the stabilization of the catalytic system, three measures of CO, CO 2 , and CH 4 were taken and an average value was calculated.The effluent gases were passed through a cold trap to condense water before being analyzed.The water level in the cold trap was low enough to prevent absorption of any gases.The analysis of evolved gases was conducted using an online GC (Trace-GC-RGA, Thermo Scientific) equipped with a thermal conductivity detector (TCD).The HayeSep Q capillary column (8  × 1/8  SS) is capable of separating CO 2 and C 1 -C 2 paraffin and the Molecular Sieve 5A plot capillary column is capable of separating O 2 , N 2 , CH 4 , and CO.During catalytic testing, carbon balances were calculated and were repeatedly between 97 and 99%.
Activity-selectivity data were obtained at steady-state conditions after 1 h of time on stream, at reaction temperatures.CO 2 conversion values ( CO 2 ) were calculated by massbalance method: CH 4 formation rate is reported as number of molecules formed per unit time and per catalyst weight (mmol h −1 g −1 cat ).Each data set was obtained with an accuracy of ±4%, from an average of two independent measurements.[53] showed that the tetragonal Ce  Zr 1− O 2 phase appears with Ce < 50 mol% (C20Z), whereas above 50 mol%, a cubic Ce  Zr 1− O 2 (C50Z and C80Z) phase is formed.With 80% Zr in our samples, the ceria peak originally at 2 ≈ 28.6 ∘ is now at 2 ≈ 30.0 ∘ , which overlaps with a zirconia line at 2 ≈ 30.1 ∘ .In addition, we detected a doublet at 2 ≈ 34.3 ∘ and 34.8 ∘ which is close to the tetragonal zirconia peaks at 2 ≈ 34.6 ∘ and 35.4 ∘ .The peak at 2 ≈ 34.9 ∘ is clearly a tetragonal zirconia line, shifted down 0.5 ∘ due to doping by small amounts of Ce.The peak with 2 ≈ 34.3 ∘ is in a region where a cubic ceria-zirconia line (shifted up from 2 ≈ 33.1 ∘ , in pure CeO 2 ) overlaps with a tetragonal zirconia-ceria line (shifted down from 2 ≈ 34.6 ∘ , in pure ZrO 2 ).This shift is indicative of change in lattice parameter, and it is evident that CeO 2 and ZrO 2 form a solid solution.The powder possesses the diffraction peaks at 2 = 30, 34.9, 49.7, and 58.5 ∘ related to the reflection planes (111), ( 200), (220), and (311) of Ce 0.2 Zr 0.8 O 2 , respectively, showing the replacement of Zr atoms for Ce.Our measured lattice parameters are similar to those from reference materials [53].Duwez and Odell [54] also obtained a tetragonal zirconia phase when high compositions of zirconia were used (around 80%), but for the sample containing 25% Zr they still obtained a cubic phase.

Results and Discussion
XRD  1.It can be seen that the Ni species dispersed well on the AC surface due to a high specific area of the support.However, the results show that the Ni particle size in 7 Ni/CeZrAC (17,39 nm) is smaller than that in 7 Ni/AC (21.82 nm) with pure AC as the support.This observation suggests that the dispersion of Ni species increases for the 7 Ni/CeZrAC catalyst due to the character of structural promoter of Ce  Zr  O  mixed oxide.Since the XRD patterns exhibit identical 2 angles, it can be said that the samples are completely reduced to metallic nickel without any detection of NiO  phases, and the experimental procedure did not alter significantly the main crystalline phases of the samples.2).BET surface areas, pore volume, and pore diameter of AC and of 7 Ni/AC reduced in H 2 at 600 ∘ C for 3 hours were listed in Table 2.It could be seen that activated carbon has a microporous structure and a developed specific surface area of 1159 m 2 g −1 with high microporous content (micro surface area is ∼1139 m 2 /g and microporous volume is ∼0.5025 cm 3 /g).The addition of nickel species resulted in slight decreases in surface areas and pore volume of the sample.This could be mainly attributed to a partial blockage of micropores by nickel species and the variation in mass

N 2 Adsorption-Desorption Analysis (Table
mes (cm density of the catalyst.A decrease in the external surface area with the Ni loading was also observed, which could suggest that Ni species may deposit on the external surface of the support.However, for all samples, the active sites of the catalysts are accessible to the reactant molecules. The textural properties of 7 Ni/CeZrAC which was reduced in H 2 at 600 ∘ C for 4 hours are also presented in Table 2.There was a strong decrease in surface area of AC when Ce 0.2 Zr 0.8 O 2 was introduced.It may be due to the deposition of Ce 0.2 Zr 0.8 O 2 on the AC surface, which blocked micropores leading to a strong decrease in micro surface area and a simultaneous increase in external surface areas and mesoporous volume.The wide pore diameter can provide favorable conditions for the reactant molecules to diffuse and transfer in the catalyst and it may be one reason for the better performance of the 7 Ni/CeZrAC in comparison to that of the 7 Ni/AC.Figures 2(c) and 2(d)) were analyzed by SEM at 300 nm and 1.0 m scales.For 7 Ni/AC it can be seen that the surface of the sample exhibits a high density block structure.SEM image showed well the existence of large cavities over the catalyst texture, likely originated from activated carbon surface (Figure 2(a)).

SEM and TEM
SEM images of 7 Ni/CeZrAC after reduction at 600 ∘ C for 4 hours were shown in Figures 2(e) and 2(f).A homogeneous distribution of spherical particles was obtained when Ce 0.2 Zr 0.8 O 2 was deposited on the AC surface.At higher magnification (Figure 2(f)), the catalyst showed morphology with spherical particles of about 50-60 nm.Further, the Ni particles could not be seen obviously on the support in SEM images, suggesting a better dispersion of Ni crystallite species that were doped into the ceria-zirconia solid solution.
TEM images of 7 Ni/AC and 7 Ni/CeZrAC after reduction at 600 ∘ C in H 2 atmosphere for 4 hours were shown in Figure 3 where black spots are Ni particles.It could be seen that Ni particles are well dispersed over Ce 0.2 Zr 0.8 O 2 layer which was deposited on the activated carbon support.The introduction of Ce 0.2 Zr 0.8 O 2 improved the formation of smaller particles.It can see easily that the particle's sizes from TEM results are in good agreement with XRD and BET analysis.

The Reducibility of the Catalysts.
TPR-H 2 was carried out to study the reduction property of the catalysts.Figure 4 shows the TPR profiles of 7 Ni/CeZrAC and 7 Ni/AC.The TPR profiles of AC and Ce 0.2 Zr 0.8 O 2 are also presented for comparison.TPR profiles for studied samples display two distinct reduction bands in the temperature range of 160-350 ∘ C which can be attributed to the reduction of nickel species and another broad reduction band in the temperature range of 350-700 ∘ C corresponding to the reduction of the supports.In order to gain more insight into the TPR results, the profiles were deconvoluted into several Gaussian peaks.In the reduction profile of Ce 0.2 Zr 0.8 O 2 three peaks around 401-614 ∘ C are attributed to the reduction peaks of the surface oxygen and the bulk oxygen in Ce 0.2 Zr 0.8 O 2 , respectively [26].According to the literature [26], the existence of reduction peaks at temperatures below 600 ∘ C for the CeO 2 is assigned to the presence of surface and subsurface oxygen atoms, which are the main ones responsible for the improved CeO 2 oxygen storage capacity.It can be seen that these peaks are shifted to lower temperatures due to the presence of nickel indicating an existence of interaction between Ni and Ce.Similarly, two peaks around 638-693 ∘ C appearing in the profile of activated carbon are assigned for the reduction peaks of surface oxygen and bulk oxygen in AC and/or functional groups in AC.The addition of Ni species shifted these peaks to lower temperatures.

The Reduction of Ni Species in Ni-AC Catalysts.
Regarding the reduction peaks of nickel species in 7 Ni/AC catalyst, it can be seen that three obvious reduction bands are observed: the first band (I) at the lowest-temperature with a maximum      around 228-231 ∘ C can be assigned to the well dispersed nickel species in the samples (may be assigned to the relatively free nickel species weakly interacting with support), which are easily reduced [29].The low temperature band, the second band (II), shows a maximum at about 275-290 ∘ C, which may be due to the reduction of dispersed nickel species [55] and the third band (III) with a maximum around 343-357 ∘ C may be related to the reduction of bulk nickel species in intimate contact with the support [56].The peak positions and their contribution are summarized in Table 3.

The Reduction of Ni Species in Ni/CeZrAC Catalyst.
It can be seen that the curve of 7 Ni/CeZrAC is similar to that for 7 Ni/AC but the first three reduction peaks slightly shift toward the higher temperatures than in the 7 Ni/AC, which indicates a higher interaction between nickel species and the support (Ce 0.2 Zr 0.8 O 2 /AC).Since Ce 0.2 Zr 0.8 O 2 and AC are not reducible at the temperature range of 160-350 ∘ C (as shown in their TPR-H 2 profiles), these first three peaks are attributed to the reduction of nickel species in the samples.Although the maximum reduction temperatures are slightly higher compared to that in 7 Ni/AC, the concentration of nickel species which can be easily reduced increases for 7 Ni/CeZrAC sample, indicating that the presence of Ce and Zr helps the dispersion of active sites and hence improves the reducibility of the sample.This attribution is in good agreement with that reported by Xu and Wang [57].
H 2 consumption of the supports and catalysts was calculated (Table 3).The obtained results show that the H 2 consumption of 7 Ni/CeZrAC catalyst (3.54 mmol g −1 ) is higher than sum of 7 Ni/AC (2.62 mmol g −1 ) and Ce 0.2 Zr 0.8 O 2 (0.64 mmol g −1 ).It has been shown that the metal-support interaction between cerium-zirconium oxides and nickel oxides promotes the reducibility of samples [58].This intimate metal-support interaction also promotes the dispersion of nickel oxide.
Based on TPR data, all samples were pretreated in H 2 at 600 ∘ C for 4 hours before measuring the catalytic activity in CO 2 hydrogenation reactions.

Catalytic Performance.
Prior to the evaluation of the studied catalyst samples, the blank test in the absence of the catalyst sample was carried out in the range of 100-500 ∘ C and GHSV = 4000 mL h −1 g −1 (STP).The results showed that the blank reactor system was relative inert; only a negligible CO 2 conversion (<1%) could be detected under experimental conditions.Another two tests in the presence of pure AC and Ce 0.2 Zr 0.8 O 2 /AC (without the presence of Ni species), respectively, were also performed under the same experimental conditions.It was found that not any CO 2 conversion and also CO or CH 4 were detected indicating that CH 4 and/or CO would be the products of CO 2 hydrogenation over studied Ni containing catalyst samples.
The catalytic activities of the samples were evaluated by analyzing the CO 2 conversion and CH 4 selectivity.In all experiments carried out only CH 4 and small amount of CO were detected at the outlet of the reactor; the carbon molar balances was about 97%.
Figures 5(a 3.5.1.The CO 2 Conversion.As seen in Figure 5 for both two samples, the amounts of CO 2 in the gas mixture decreased as temperature increased.The temperature at which the amount of CO 2 started going down was 200 ∘ C over 7 Ni/AC and 170 ∘ C over 7 Ni/CeZrAC.These phenomena indicated the conversion of CO 2 occurred and the conversion gradually increases with the temperature up to 450 ∘ C (over 7 Ni/AC) and 400 ∘ C (over 7 Ni/CeZrAC), but as further rise in temperature, the CO 2 conversion starts going down.

The CH 4 and CO Formation.
There were two temperature ranges for product selectivity.At low temperature range of 200 ∘ C to 400 ∘ C over 7 Ni/AC and 170 ∘ C to 350 ∘ C over 7 Ni/CeZrAC, the formation of CH 4 was dominant; no alcohols or other hydrocarbons could be expected to be formed.CO formation was accompanied with CH 4 but very slightly.A further increase in the temperature (up to 500 ∘ C) will result in the stable increase in CO formation with the decrease of CO 2 conversion and the decrease of selectivity to methane formation as well.These phenomena are related to the thermodynamic nature of the CO 2 hydrogenation reaction because CO formation can occur mostly by the reversed water gas shift reaction (RWGS) and a small contribution depending on temperature from steam reforming (SR) of methane.
These observations are in good agreement with the work done by Grac ¸a et al. [29] and by Janke et al. [10].6), and it reached the maximum conversion value even at only 350 ∘ C. In the temperature range of 150-350 ∘ C no CO was detected at the outlet indicating a 100% for CH 4 selectivity (Figure 5(b)).This positive effect which shows the improvement of catalyst performance resulted from Ce-Zr well incorporation with Ni and AC surface.

The Effects of the
It has been claimed in the literature that (Ce-Zr) species can activate CO 2 molecules and reduce them into CO due to the great mobility of the oxygen atoms.These CO species can be subsequently hydrogenated into methane.In the work done by Sharma et al. [13] Ru-doped ceria, Ce 0.95 Ru 0.05 O 2 , prepared by a combustion method showed higher catalytic activity for CO 2 methanation than 5 wt% Ru/CeO 2 and the conversion of CO 2 and selectivity of CH 4 were 55% and 99%, respectively.By feeding 13% CO 2 , 54% H 2 , and 33% Ar at 450 ∘ C and GHSV = ca.10,000 h −1 , Wang et al. [25] indicated that Ni/Ce 0.5 Zr 0.5 O 2 catalysts prepared by impregnation method possessed the highest activity for CO 2 hydrogenation.It can attain 73% conversion at 300 ∘ C and have a CH 4 selectivity of 100%.
The Ni/Ce 0.2 Zr 0.8 O 2 /AC catalyst prepared in the present work had an excellent activity for CO 2 methanation at lower temperatures and a high CH 4 selectivity of 100%.TPR-H 2 characterization indicated the intimate interaction between the metal and the support that could promote the reduction of Ce 0.2 Zr 0.8 O 2 , while the strong interaction inhibits the reduction of Ni species.Swalus et al. [21] indicated that nickel supported on AC is able to activate high amount of hydrogen, while Rynkowski et al. [38] reported that Ce 0.2 Zr 0.8 O 2 could supply the surface oxygen sites for CO 2 adsorption.Also, our previous theoretical study [51] showed that nickel plays an important role in the dissociative adsorption of CO 2 .In that work the adsorption of carbon dioxide on AC was studied in two steps: (i) GCMC (grand canonical ensemble Monte Carlo) simulation to determine the most favorable adsorption positions; (ii) these configurations optimized using the DFT and DFT-D2 methods.Results obtained from the GCMC simulation showed that the CO 2 molecule is most favorably physically adsorbed on the surface of AC.The preferred configurations were then optimized to determine the adsorption energy of CO 2 on AC (Eads).The results obtained using the DFT and DFT-D2 methods were −27.3 kJ/mol and −46.9 kJ/mol, respectively, which indicate that CO 2 is easily adsorbed on the AC.When Ni was doped on the AC surface, the CO 2 molecule was chemically adsorbed and the C-O bond is strongly activated after the adsorption of CO 2 .The adsorption process of CO 2 did not involve a transition state.Our calculated results showed that CO 2 adsorption and dissociation are the first steps in the mechanism of CO 2 .Jacquemin et al. [8] had the same statement that the first step of the mechanism in the methanation reaction could be the chemisorption of CO 2 on the catalyst and followed by the dissociation of CO 2 into CO and O adsorbed on the surface.From obtained results we suggested that using AC as a carrier may lead to a significant increase of the partial pressure of CO 2 on the surface of the catalyst.In other words, the conversion of CO 2 with high efficiency can be carried out at unusually low pressures due to the increased CO 2 partial pressure on the AC surface.Our results give an evidence that at low temperature and at atmospheric pressure, it is possible to obtain methane from hydrogenation of CO 2 when using an adequate catalyst.The work done by Beuls et al. [7] shows the same conclusion, but the catalyst used was Rh/-Al 2 O 3 .

Conclusion
The present work investigated the correlation between structural properties and catalytic performance of 7 Ni/AC and 7 Ni/Ce 0.2 Zr 0.8 O 2 /AC catalysts for CO 2 methanation reaction.The characterization of the samples by XRD,SEM, TEM, BET, and H 2 -TPR techniques indicated that the dispersion of Ni species on the AC or Ce 0.2 Zr 0.8 O 2 /AC was influenced by the structure of the supports and Ce 0.2 Zr 0.8 O 2 /AC could stabilize the nickel species more effectively than AC.The characterized results suggested that Ni species interacted with Ce 0.2 Zr 0.8 O 2 /AC more strongly than that with AC, and compared with the AC support the Ce 0.2 Zr 0.8 O 2 /AC support had greater ability to facilitate the reduction of Ni species.The "synergistic effect" between the metal active sites (Ni), the promoter (Ce 0.2 Zr 0.8 O 2 ), and the support (AC) could promote the activation of adsorbed CO 2 ; therefore 7 Ni/Ce 0.2 Zr 0.8 O 2 /AC showed the higher activity toward hydrogenation of CO 2 to methane than 7 Ni/AC.Our results suggest that the use of dissociative chemisorption of CO 2 could probably allow decreasing reaction temperature and the methanation of CO 2 at low temperature could be a solution for the control of increasing emission of CO 2 .

3. 1 .
XRD Characterization.The identification of the crystalline phases was carried out by XRD.The XRD patterns of 7 Ni/AC after reduction are presented in Figure 1.After reduction at 600 ∘ C in hydrogen atmosphere for 4 hours, all the reduced samples showed prominent peaks of metallic Ni at the 2 = 44.2∘ and 51 ∘ which are indexed to (111) and (200) diffractions planes, respectively.This matched the standard data for a cubic structure Ni (JCPDS 96-151-2527).No other peaks appear.It can be seen that the thermal treatment in H 2 at 600 ∘ C is sufficient for producing bulk o Ni crystallites from nickel containing species.The XRD patterns of mixed oxide Ce 0.2 Zr 0.8 O 2 and 7 Ni/CeZrAC after reduction were also displayed in Figure 1.The formation of Ce 0.2 Zr 0.8 O 2 on the AC was proved by XRD characterization.Phase transitions occurring in Ce  Zr 1− O 2 depend on their composition.For pure ZrO 2 (Z) the diffraction peaks at 2 ≈ 30.3 ∘ , 34.6 ∘ , and 35.4 ∘ can be assigned to the tetragonal ZrO 2 structure (JCPDS 79-1769) and for pure CeO 2 (C) the diffraction peaks at 2 ≈ 28.7 ∘ and 33.1 ∘ can be assigned to the cubic CeO 2 structure (JCPDS 65-5923).The work done by Hori et al.
Images.Morphologies of pure AC (Figure 2(a)) of mixed oxide Ce 0.2 Zr 0.8 O 2 (Figure 2(b)) and of catalyst sample 7 Ni/AC after reduction at 600 ∘ C for 4 hours (

Figure 3 :
Figure 3: TEM images of reduced catalyst samples.
) and 5(b) present the CO 2 conversion and CH 4 and CO formation over 7 Ni/AC and 7 Ni/CeZrAC samples as a function of the reaction temperature.

Figure 6 :
Figure 6: The comparison in CO 2 conversion between two Ni/AC samples with and without Ce 0.2 Zr 0.8 O 2 : 7 Ni/AC and 7 Ni/CeZrAC.
Catalyst with Ce 0.2 Zr 0.8 O 2 /AC as the Support.The mixed oxide Ce 0.2 Zr 0.8 O 2 was prepared using hydrothermal method as in the work of Pham et al.Zr 0.8 O 2 was deposited on AC by suspension method: 5 g AC grains were immersed in 30 mL aqueous slurry of 20 wt% of Ce 0.2 Zr 0.8 O 2 powder, 20 vol% molten (70 ∘ C) Brij 56 (Sigma Aldrich, Steinheim, Germany), and 2.8 M HNO 3 and then dried and air blown.This coating and drying process was performed five times before calcination at 200 ∘ C for 4 h.The amount of Ce 0.2 Zr 0.8 O 2 on AC was determined by weighting the sample before (  ) and after (  ) the loading.The wt% loading was calculated as follows: wt% = ((  −   )/  ) × 100.
2 reacted moles of CO 2 supplied × 100 Selectivity for methane (%) = moles of CH 4 formed moles of CO 2 reacted × 100 pattern of 7 Ni/CeZrAC shows characteristic peaks of metallic Ni (2 = 44.2∘ and 51 ∘ ).There are also other diffraction peaks (at the 2 values of 30, 49.7, and 59.6 ∘ ) matching the standard data for a tetragonal mixed oxide Ce 0.2 Zr 0.8 O 2 (ICDD Card number 80-0785).The existence of ZrO 2 and CeO 2 or other species were not observed in XRD pattern of 7 Ni/CeZrAC.The presence of only tetragonal structure in the Ce 0.2 Zr 0.8 O 2 sample and in 7 Ni/CeZrAC as well indicates that Ce and Zr are highly homogeneously distributed.The approximate average crystallite sizes of mixed oxide Ce 0.2 Zr 0.8 O 2 in 7 Ni/CeZrAC sample and of pure Ce 0.2 Zr 0.8 O 2 were calculated by Scherrer's equation that indicates similar values.The approximate average crystallite sizes of Ni in catalyst samples were calculated from the (111) peak at 44,2 ∘ in the XRD patterns and Scherrer equation and are presented in Table

Table 1 :
Lattice parameters from XRD results and crystallite size of Ni () from Scherrer equation.

Table 3 :
max and consumed H 2 for TPR patterns over studied catalysts.
Mixed Oxide Ce 0.2 Zr 0.8 O 2 Addition.A comparison in CO 2 conversion over 7 Ni/AC and 7 Ni/CeZrAC was made and shown Figure 6.It can be seen that the addition of solid solution Ce 0.2 Zr 0.8 O 2 is responsible for improvement of both CO 2 conversion and CH 4 selectivity: the conversion of CO 2 started at a lower temperature (170 ∘ C) compared to that of 7 Ni/AC sample (Figure