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Influence of the Catalyst Preparation Method, Surfactant Amount, and Steam on CO2 Reforming of CH4 over 5Ni/Ce0.6Zr0.4O2 Catalysts
Thitinat Sukonket,, Ataullah Khan, Bappy Saha, Hussameldin Ibrahim, Supawan Tantayanon, Prashant Kumar, and Raphael Idem*,

Process Systems Engineering, Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan S4S 0A2, Canada Green Chemistry Research Lab, Faculty of Science, Department of Chemistry, Chulalongkorn University, Bangkok 10330, Thailand HTC Purenergy Inc., #150-10 Research Drive, Regina, Saskatchewan S4S 7J7, Canada ABSTRACT: A series of ceria-zirconia mixed oxide supports with nominal composition Ce0.6Zr0.4O2 were synthesized by two different routes, namely, a surfactant-assisted route and a coprecipitation route. Among the supports obtained by the surfactant-assisted route, dierent surfactant/metal molar ratios (namely, 1.25, 0.8, and 0.5) were employed to study the inuence of the surfactant amount on the catalyst performance. A nominal 5 wt % Ni was impregnated on the supports by a wet impregnation method. These catalysts were evaluated for CO2 reforming of CH4 in both the presence and absence of steam. The textural, structural, and physicochemical characteristics of the catalysts were thoroughly investigated with the help of various bulk and surface characterization techniques. The activity results indicate the superior nature of the catalysts obtained by the surfactant-assisted route over the one obtained by coprecipitation. Also, within the limits of the surfactant ratios used, the amount of surfactant employed during the course of support preparation seems to aect the activity, with catalysts prepared with the higher surfactant/metal molar ratio exhibiting better activity and enhanced stability. Structure-activity relationships (SARs) were formulated for some of the characteristics in order to explain the marked dierence in activity between the catalysts obtained by the surfactant-assisted and coprecipitation methods and between the catalysts prepared by the surfactant-assisted route but with dierent surfactant/metal molar ratios. The SARs helped to identify that high oxygen storage capacity, high surface area, high reducibility, higher nickel surface area, better nickel dispersion, and higher surface nickel content are necessary for good performance in the CO2 reforming of CH4. On the whole, catalysts obtained by the surfactant-assisted route exhibit a reasonably good performance in the CO2 reforming reaction but were prone to deactivation in the presence of steam. The inherent hydrophilic nature of the ceria-zirconia support is the main cause for the apparent deactivation in the presence of steam.

1. INTRODUCTION The CO2 reforming of CH4 to produce synthesis gas has attracted attention from academia and industry in recent years because this reaction involves gases that are intimately related to the greenhouse eect and energy supply. This reaction directly converts two potent greenhouse gases (CH4 and CO2) to synthesis gas with a low H2/CO ratio (1), which satises the requirement of many important processes, such as FischerTropsch synthesis and carbonyl production.1 However, CO2 reforming uses a high C/H feedstock, which results in carbon deposition on the catalyst by CO disproportionation (2CO f CO2 C) and/or methane decomposition (CH4 f 2H2 C) reactions. This problem has become the major issue in CO2 reforming of methane.2 Thus, current intense research eorts have been focused in the development of catalysts that show high activity and are also resistant to carbon formation and sintering. With its relative availability, low cost, and activity comparable to a noble metal catalyst, nickel-based catalysts have shown good potential as a catalyst for the reforming of methane.3 Nickel has been supported on various materials such as MgO,4,5 Al2O3,6,7 SiO2,8,9 (MgFe)2SiO4,10 CeO2,11 ZrO2,12 and Ce1-xZrxO2.13-19 Currently, the Ce1-xZrxO2 solid solution is considered as a promising support13-19 for nickel-based catalysts. The addition
r 2011 American Chemical Society

of ZrO2 to CeO2 has been found to improve the oxygen storage capacity (OSC), redox property, thermal stability, and catalytic activity.1,13,14,16,20,21 Moreover, the zirconium content aects the structure and redox properties of the ceria-zirconia mixed oxides. Usually, there are two phases (tetragonal and monoclinic) in the CexZr1-xO2 samples with x e 0.5.22 However, only a cubic uorite phase is formed in the CexZr1-xO2 samples when x is higher than 0.5.23 Generally, CexZr1-xO2 solid solutions where 0.8 > x > 0.6 are preferred for catalytic applications. Several methods have been used to prepare CexZr1-xO2 solid solutions for catalytic applications. These include the high-temperature ring or high-energy milling of a mixture of the oxides,24,25 coprecipitation,1,20-22,26-28 sol-gel techniques,13-16 and a surfactant-assisted templating route.29-33 Among these methods, the surfactant-assisted route, a modied coprecipitation assisted with the surfactant, has attracted considerable interest because of its eective soft template eect, reproducibility, and simplicity.29 This method can be used to prepare the solid solutions with high surface area and thermal stability that are essential for hightemperature catalytic application.32,33 The Ce0.6Zr0.4O2 systems
Received: September 2, 2010 Revised: January 5, 2011 Published: February 04, 2011
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sample Ce0.6Zr0.4O2 5% Ni/Ce0.6Zr0.4O2 Ce0.6Zr0.4O2 5% Ni/Ce0.6Zr0.4O2 Ce0.6Zr0.4O2 5% Ni/Ce0.6Zr0.4O2 Ce0.6Zr0.4O2 5% Ni/Ce0.6Zr0.4O2

a

preparation routea CP WI SA WI SA WI SA WI

acronym CZ NCZ CZ(1.25) NCZ(1.25) CZ(0.8) NCZ(0.8) CZ(0.5) NCZ(0.5)

Ni surface average CTAB/ pore average pore volume/ OSC Ni [Ce Zr] BET surface volume pore BET surface [mol of O dispersion area [m2 (g of crystallite size molar ratio area (m2 g-1) (cm3 g-1) diameter () area (10-9 m) (g of cat.)-1] (%) DNi cat.)-1] SNi CeO2 (nm)b n/a n/a 1.25 1.25 0.8 0.8 0.5 0.5 93 59 201 184 203 169 232 215 0.06 0.06 0.3 0.2 0.4 0.3 0.4 0.3 32 51 41 41 57 53 51 51 0.6 1.0 1.5 1.1 2.0 1.8 1.7 1.4 866 4.2 1093 7.4 1031 6.4 937 5.4 1.8 2.0 2.5 1.4 4.0 3.8 4.6 4.1 4.3 4.2 4.2 3.2

CP = coprecipitation route; WI = wet impregnation route; SA = surfactant-assisted route. b Calculated using the Debye-Scherrer equation. gelatinous yellow-brown colloidal slurry. The slurry was stirred for 60 min in a glass reactor, subsequently transferred into Pyrex glass bottles, sealed, and aged hydrothermally in autogenous pressure conditions for 5 days at 90 C. After this timeframe, the bottles were cooled and the resulting precipitate was filtered and washed repeatedly with warm DI water. The resulting cakes were oven-dried at 120 C overnight and finally calcined at 650 C for 3 h in flowing air. Similarly, pristine CeO2 was prepared by the surfactant-assisted route following the exact procedure detailed above. The Ce0.6Zr0.4O2 mixed oxide support was also prepared by the conventional coprecipitation method, wherein calculated amounts of Ce(NO3)3 3 6H2O and ZrO(NO3)2 3 2H2O salts were dissolved in DI water and hydrolyzed with aqueous ammonia until precipitation was complete. The resulting precipitate was ltered, oven-dried at 120 C overnight, and nally calcined at 650 C for 3 h in an air environment. A nominal 5 wt % Ni was loaded over the above-prepared supports by a standard wet impregnation method. In a typical impregnation, about 14 g of the catalyst support was immersed in 128 mL of a 0.1 M Ni(NO3)2 solution (99.999% purity, Aldrich). The mixture was subjected to slow heating under constant stirring in a hot water bath so as to remove the excess water; the dried powders thus obtained were calcined at 650 C in air for 3 h. Pristine NiO in bulk form was prepared by a solidstate preparation route, wherein a known amount of Ni(NO3)3 3 6H2O salt (99.999% purity, Aldrich) was calcined at 650 C for 3 h in owing air in order to yield bulk crystalline NiO. For the sake of brevity, the supports and corresponding catalysts employed in the present investigation are abbreviated as detailed in Table 1. For instance, CZ and NCZ correspond respectively to Ce0.6Zr0.4O2 and 5 wt % Ni/Ce0.6Zr0.4O2, while for the samples obtained by the surfactant-assisted route, the numbers in parentheses correspond to the CTAB/[Ce Zr] (surfactant-to-metal) molar ratio. 2.2. Catalyst Characterization. Surface Area and Pore Size Distribution Analysis. The Brunauer-Emmett-Teller (BET) surface area and pore size distribution analyses for all catalysts were obtained by N2 physisorption at liquid-N2 temperature using a Micromeritics ASAP 2010 apparatus. Prior to analysis, all of the samples were degassed overnight at 180 C under vacuum. The pore size distribution and average pore volume were analyzed using the desorption branch of the N2 isotherm. Each sample was analyzed by N2 physisorption at least twice in order to establish repeatability. The error in these measurements was e1%. Metallic Surface Area and Metal Dispersion Measurements. The metallic surface area and metal dispersion in the catalyst samples were estimated by H2 chemisorption at 35 C using a Micromeritics ASAP 2010C instrument. Prior to analysis, the catalyst samples were dried at 120 C and then reduced in situ in flowing H2 gas (UHP grade) at 700 C for 3 h (in order to mimic the reduced state formed during the course of a typical catalytic run) followed by evacuation at 700 C for 1 h
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have already been identied by our group as a promising support material for nickel-based catalysts for the CO2 reforming process.32,33 It is reported that 5% Ni/Ce0.6Zr0.4O2 prepared by the surfactant approach is a good catalyst for CO2 reforming of CH4 with stable activity when used for 100 h at 650 and 700 C, while at 800 C, its activity remained stable when used for more than 230 h.32-34 However, nickel-based catalysts are readily deactivated by carbon deposition at low-temperature operating conditions. Much eort has been devoted toward coke suppression in the case of nickel-based catalysts. Recently, the addition of a small amount of steam to the dry reforming feedstock was attempted in order to eliminate carbon formation.2,35-45 Hence, the simultaneous steam and carbon dioxide reforming of methane, known as the mixed reforming reaction, allows limited control of the H2/ CO ratio while overcoming carbon deposition. In our previous study,32,33 a surfactant/metal molar ratio of 1.25 was used. Although it yields an excellent catalyst, the waste material generated during the course of support preparation was large. In the present study, we are also looking at the potential to develop nickel-based catalysts supported on carriers prepared using the surfactant-assisted route with optimal utilization of a surfactant, thereby reducing the generation of chemical wastes and, thus, the production costs. Accordingly, Ce0.6Zr0.4O2 supports were prepared by the surfactant-assisted route with dierent surfactant/metal molar ratios. The catalytic activity of the resulting catalysts when 5 wt % Ni was impregnated on these supports was examined for CO2 reforming of CH4 in both the presence and absence of steam and compared with those of 5 wt % Ni impregnated on supports prepared by the conventional coprecipitated method. The results of these comparisons are presented and discussed in this paper.

2. EXPERIMENTAL SECTION
2.1. Catalyst Preparation. In order to prepare each Ce0.6Zr0.4O2 mixed oxide support by the surfactant-assisted route, appropriate quantities of Ce(NO3)3 3 6H2O (99% purity, Aldrich) and ZrO(NO3)2 3 H2O (99.9% purity, Alfa Aesar) precursor salts were dissolved in deionized (DI) water. Separately, a calculated amount of cetyltrimethylammonium bromide (CTAB; g98% purity, Sigma) was dissolved in DI water at 60 C. The metal nitrate solution was then added to the surfactant solution to obtain a mixture solution. The molar ratios of [CTAB]/ [Ce Zr] were 1.25, 0.8, and 0.5. Aqueous ammonia [28-30% (w/w); reagent grade, ACS-Pur] was gradually added to the aforementioned mixture solution under vigorous stirring until precipitation was complete (pH 11.8). The addition of ammonia induced precipitation of a

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Figure 1. (A) N2 isotherms and (B) pore volume versus pore diameter distribution of the 5% Ni/Ce0.6Zr0.4O2 catalysts obtained by the surfactantassisted route. (C) N2 isotherms and (D) pore volume versus pore diameter distribution of the NCZ(1.25) catalyst calcined at dierent temperatures. before cooling down to 35 C. The metallic surface area (SNi) was calculated with the help of the following expression: SNi 13:58 10-20 NM m2 g of cat:-1 where NM is the number of hydrogen molecules adsorbed in the monolayer per gram of catalyst. The above expression was derived by considering the surface occupied per atom of nickel as 6.49 2 atom-1 (considering the density of nickel as 8.91 g cm-3 and a face-centeredcubic lattice) and the adsorption stoichiometry as two surface nickel atoms per hydrogen molecule. The nickel dispersion (D%) was then calculated as the percentage of surface nickel atoms with respect to the total nickel atoms in the catalysts.46 The H2 chemisorption analysis was repeated for a few of the samples in order to check reproducibility. The error in these measurements was <1%. X-ray Diffraction (XRD) Measurements. Powder XRD patterns were recorded on a Bruker Discover diffractometer using nickel-filtered Cu KR (0.154 056 nm) as the radiation source. The intensity data were collected over a 2 range of 10-90 with a step size of 0.02 using a
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counting time of 1 s per point. Crystalline phases were identified through comparison with the reference data from ICDD files. The average crystallite size of CeO2 was estimated with the help of the Debye-Scherrer equation using the XRD data of all prominent lines 111, 200, 220, and 311. Temperature-Programmed Reduction (TPR) Measurements. H2TPR of various catalyst samples was performed on a Quantachrome ChemBET 3000 unit equipped with a thermal conductivity detector (TCD). For all of the samples (except pristine NiO) investigated by TPR, exactly the same amount was analyzed so as to make comparison possible. Prior to TPR measurements, the samples were degassed at 180 C in an inert atmosphere (N2 UHP grade) for 2 h. The reducibility of the supports and that of the catalysts prepared in the current study were studied by the TPR technique in the temperature range from ambient to 1050 C at a heating rate of 15 C min-1, using 5% H2/balance N2 as the reactive gas (flow rate = 45 sccm). The total reactive gas consumed during TPR analysis was measured. The H2 uptake as a function of the TCD response versus temperature was used to plot Figure 4. For reference purposes, TPR profiles of pristine NiO and CeO2 were also
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studied. A few samples were analyzed by TPR at least twice in order to establish reproducibility. The error in the Tmax values was found to be less than (4 C. Raman Analysis. The Raman analyses were performed on a Renishaw inVia Raman microscope using a Ar laser (Spectra Physics) operating at 514.5 nm. The laser beam (10 mW at the laser) was focused onto a pelletized sample using a Leica 20X NPLAN objective (NA = 0.40). The Raman spectra were acquired using a 10 s detector acquisition time, and the spectra were accumulated to achieve sufficient signal-tonoise intensities. The spectra were baseline-corrected using the Renishaw Wire V3.1 software provided with the instrument. The wavenumbers obtained from the spectra are accurate to within 2 cm-1. X-ray Photoelectron Spectroscopy (XPS) Measurements. The XPS measurements were performed on a Leybold MAX 200 X-ray photoelectron spectrometer using Al KR (1487 eV) radiation as the excitation source. Prior to analysis, the samples were outgassed in a vacuum oven overnight. Charging of the samples was corrected by setting the binding energy (BE) of the adventitious carbon (C 1s) at 285 eV.47 XPS analysis was performed at ambient temperature and at pressures typically on the order of <10-9 Torr. Pass energies of 192 and 48 eV were used for survey scan and narrow scan measurements, respectively. All binding energies quoted in this study were measured within a precision of (0.1 eV. The quantitative surface atomic composition was determined by standard methods. OSC Properties. The oxygen storage/release capacity of the support powders was measured using thermogravimetry under cyclic oxidative/ reductive excursions. A known amount of the sample (50 mg) was loaded into the thermogravimetric analyzer (Setaram TG/DSC111). The sample was subjected to reduction/oxidation cycles at 800 C (temperature employed for the catalytic activity evaluation) using the following reactive gas mixtures: 5% H2 in N2 and 5% O2 in N2, respectively. Prior to every experiment, the catalyst sample was heated to 800 C in an inert atmosphere (N2 UHP) at a ramp rate of 15 C min-1 and maintained at 800 C for 1 h, after which cyclic reduction/oxidation was carried out for 1 h each at 800 C. The flow rate of all of the gas mixtures was maintained constant at 30 sccm. The weight loss during the reduction cycle and the weight gain during the oxidation cycle were used to calculate the total OSC of the Ce0.6Zr0.4O2 support powders. The OSC tests were repeated three times on each sample, in order to establish concurrence, and it was found to be precise within the limit of (2% error. 2.3. Activity Evaluation. Activity evaluation studies were carried out in a packed-bed tubular reactor (1/2 in. i.d.) made of Inconel 625. The reactor was placed vertically inside a programmable tubular furnace (Zesta Engineering), which was heated electrically. All of the gases were regulated through precalibrated mass (gas) flow controllers with a digital readout unit (Aalborg Instruments), and a constant gas flow of 100 sccm was maintained during the course of the whole experiment. In a typical experiment, 160 mg of 0.3-mm-sized catalyst particles was mixed with 7.6 g of 0.3-mm-sized quartz sand to form a bed of 8.8 cm height. The catalyst bed temperature was measured by means of a sliding thermocouple dipped inside the catalyst bed. Prior to each run, the catalyst was activated in situ by reduction at 700 C for 3 h using a gas mixture of 5 vol % H2 in N2 (flow rate = 100 sccm). The selection of the reduction temperature was based on the maximum Tmax obtained for nickel from TPR experiments. The premixed feed gas composed of 40:40:20 (vol %) CH4/CO2/N2 was fed at a constant feed rate of 100 sccm. The N2 gas in the feed was used as an internal standard for mass balance measurements. A stoichiometric amount of water was used in the case of steamassisted CO2 reforming runs, and the water feed rate was regulated through a motorized syringe pump (Kd science). The activity evaluation tests were performed at two different temperatures, namely, 800 and 700 C. In order to approach plug-flow conditions and minimize backmixing and channeling, certain operating criteria as prescribed in our previous publications were used.32,33 Accordingly, the ratio of the
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catalyst bed height to the catalyst particle size (L/Dp) was 293, and the ratio of the internal diameter of the reactor to the particle size (D/Dp) was 42. The product reformate stream coming from the reactor was passed through a series of heat exchangers and an ice-cooled knockout trap to condense water, after which the product gases were analyzed with an online gas chromatograph/TCD (Agilent 6890 N) equipped with Hayesep Q and molecular sieve A columns. Some tests were repeated in order to check for reproducibility. The maximum errors for both conversion and selectivity were <1%.

2.4. Equations Used for Calculation of the Conversion, Selectivity, and Yield. The CH4 conversion, CO2 conversion, H2
yield, and H2 selectivity (all calculated in units of mol %) are defined as follows: Without steam : CH4 CO2 T 2H2 2CO With steam : CH4 2H2 O T 4H2 CO2 Without steam % CH4 conversion FCH4,in -FCH4,out 100 FCH4,in FCO2,in -FCO2,out 100 FCO2,in 3 1 2

% CO2 conversion % H2 yield % H2 selectivity With steam

4 5 6

FH2,out 100 0:5 FCH2,in

FH2,out 100 2FCH4,in -FCH4,out

% CH4 conversion1

FCH4 used in 1 100 FCH4,in

% CH4 conversion2

FCH4,in -FCH4 used in 1 - FCH4,retained 100 FCH4,in

8 % CH4 conversiontotal % CH4 conversion1 % CH4 conversion2 9 % CO2 conversion % H2 selectivity FCO2 used in 1 100 FCO2,in 10 11

FH2,out 100 FH2 from 1 FH2 from 2 Fi,out Ftotal :ci

where Fi,in or Fi,out is the flow rate of each component in the feed or effluent, Ftotal represents the total flow rate of the gaseous effluent, and ci is the molar fraction of component i in the gaseous effluent. Turnover frequencies (TOFs) were calculated from the methane conversions by assuming that all surface nickel species or sites accessible by the H2 chemisorption technique were active. The TOF (time-1) of the reforming reaction is dened as the rate of conversion of CH4 (mol s-1) divided by the moles of accessible surface nickel atoms present in the reactor, and the corresponding results are presented in Figures 6, 8, and 9.
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3. RESULTS AND DISCUSSION

3.1. Catalyst Characteristics. The textural characteristics of the supports and those of the catalysts prepared in this study are summarized in Table 1. From Table 1, it is noted that the supports and catalysts prepared by the surfactant-assisted route exhibit larger specific surface area and pore volume compared to the supports and catalysts prepared by the coprecipitation method. Similar results were reported by Terribile et al.,29 wherein the higher surface areas were obtained as a result of interaction between a hydrous mixed-metal hydroxide gel and cationic surfactants under basic conditions. At pH g 11.0, the surface hydroxyl protons [CeZr(O-H)4] are exchanged with the cetyltrimethylammonium cation [(C16H33)N(CH3)3], resulting in the incorporation of the surfactant cations into a hydrous ceria-zirconia mixed hydroxide oxide gel. This incorporation decreases the interfacial energy and eventually decreases the surface tension of water that exists in the hydrous support pores. As a result, the degree of shrinkage and pore collapse that would occur in the hydrous support during drying and calcination is reduced, thereby imparting a high surface area to the sample. The current results reveal that the supports obtained by the surfactant-assisted route possess very high surface areas (Table 1) and changes in the surfactant/metal molar ratios do not seem to have a strong influence over the resultant surface area. Upon impregnation of the supports obtained by surfactant-assisted and coprecipitation routes, with a nominal 5 wt % Ni, a loss in the surface area can be seen, as shown in Table 1. This is a general phenomenon observed in the case of supported catalysts when an active component is impregnated over its surface and into its pores. The observed decrease is mainly due to penetration of the dispersed nickel oxide into the pores of the support, thereby narrowing its pore diameter and blocking some of the pores.32 Likewise, there can be instances wherein pore collapse could lead to increases in the pore volume and pore diameter, as could be noted with the coprecipitated sample (Table 1.). The N2 isotherms of catalysts obtained from supports prepared by the surfactant-assisted route are shown in Figure 1A. The isotherms belong to the type IV class and exhibit type H2 hysteresis. The isotherms point to the existence of mesoporosity with network eects in the analyzed catalysts. Additionally, the pore volume versus pore size distribution patterns of the catalysts obtained by the surfactant-assisted route are shown in Figure 1B. Analysis of the observed trends in the pore volume distribution patterns reveals that the size of the existing pores is not dispersed over a wide range, and it is, in fact, limited to a narrow range of 2-10 nm. The average pore sizes reported in Table 1 are in good agreement with those in Figure 1B. Furthermore, it is noted that pores of >10 nm diameter are nonexistent in the analyzed catalyst samples. The calcination temperature (650 C) employed in the current study is lower than the operating temperature of the catalytic studies (700 and 800 C). In order to evaluate the thermal stability of the catalyst at reaction conditions (essentially the potential for sintering under reaction conditions), two samples of the 650 C calcined NCZ(1.25) catalyst were recalcined, one at 700 C and the other at 800 C for 3 h in owing air. The recalcined samples were analyzed by the N2 physisorption technique. The results are presented in Table 2 and are compared with the results obtained for the 650 C calcined sample. As is evident from Table 2, there is a loss in the surface area and porosity as the temperature increases. This change is considered
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Table 2. Eect of the Calcination Temperature on the Textural Characteristics of NCZ(1.25)

average calcination temperature duration (C) (h) BET surface area (m2 g-1) pore volume (cm3 g-1) pore diameter () pore volume/ BET surface area (10-9 m)

5% Ni/Ce0.6Zr0.4-NCZ(1.25) 650 700a 800a

a

3 3 3

184 153 102

0.25 0.22 0.15

41 47 51

1.1 1.4 1.5

Using the 650 C calcined NCZ(1.25) sample.

to be due to the loss of surface capping hydroxyl and oxygen ions from the catalyst, thereby opening up the pores with a corresponding decrease in the surface area (see Table 2). The major eect of the temperature appears to be that the pore volume/ surface area value increases with an increase in the temperature (Table 2). On the other hand, the N2 physisorption isotherms of the NCZ(1.25) catalyst samples calcined at dierent temperatures (shown in Figure 1C) show that the isotherms for the 700 and 800 C calcined samples are similar to the isotherm for the 650 C calcined sample, and all three isotherms can be categorized into the type IV isotherm. The type IV isotherm is generally associated with mesoporous materials. Analysis of the pore volume versus pore size distribution patterns (Figure 1D) of the above calcined samples reveals that a majority of the pores are concentrated in the size range of 4-5 nm. Thus, it can be concluded that, at higher temperature reaction conditions, the catalyst sample retains its mesoporosity, and there is no sintering because the latter would imply a loss of surface area due to agglomeration and the collapse of the pore structure of the material. The OSC is the ability of the catalysts to undergo cyclic reduction/oxidation under the given operating conditions. This unique feature in Ce0.6Zr0.4O2 solid solutions is due to their inherent ability to easily and reversibly reduce to O2-decient nonstoichiometric compounds with a nominal composition Ce0.6Zr0.4O2-x (where 0 < x < 0.178) when exposed to reducing atmospheres and subsequently regain their original stoichiometry when exposed to oxidizing atmospheres. Interestingly, Ce0.6Zr0.4O2 solid solutions retain the same uorite crystal structure in both reduced and oxidized states, thus facilitating the redox process.48,49 The OSC measurements obtained for various Ce0.6Zr0.4O2 supports investigated in the current study are shown in Table 1. The Ce0.6Zr0.4O2 supports prepared by the coprecipitation and surfactant-assisted routes with varying surfactant/metal ion molar ratios exhibit variable OSC functionality (Table 1), which implies that they dier in their redox properties. Supports with higher OSC values will possess a highly facile Ce4 S Ce3 redox couple compared to the ones with lower OSC values. The OSC of the support obtained by the surfactantassisted route is higher than the OSC of supports obtained by the coprecipitation route. Within the family of supports obtained by the surfactant-assisted route, it is observed that the OSC increases with increasing surfactant/metal molar ratios (Table 1). Recent literature reports suggest that the OSC of the ceria-zirconia solid solution is independent of its specic surface area.48,49 The XRD patterns of the supports and catalysts investigated in the current study are shown in Figure 2 along with the XRD proles of pristine ceria and nickel oxide samples. The XRD
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Figure 2. XRD patterns of Ce0.6Zr0.4O2 supports and 5% Ni/Ce0.6Zr0.4O2 catalysts.

prole of pristine ceria is characteristic of the presence of a cubic uorite-type crystal structure. The diraction patterns of the supports and catalysts exhibit diraction patterns exactly the same as that of pristine ceria, thus conrming the existence of a single-phase cubic uorite-type structure. A distinct shift toward higher 2 values could be noted in the case of Ce0.6Zr0.4O2 and 5Ni/Ce0.6Zr0.4O2 samples (2 29.0), when compared with pure CeO2 (2 = 28.65). The shift in the peak positions can be attributed to the structural distortion caused by the substitution of smaller Zr4 ions (0.84 ) in place of larger Ce4 ions (0.97 ) in the cubic uorite lattice.47 The XRD prole of pristine NiO was used to identify the existence or nonexistence of crystalline NiO in the nickel-impregnated catalyst samples. 5% Ni/Ce0.6Zr0.4O2 prepared by the coprecipitation method showed the presence of crystalline NiO, while the 5% Ni/Ce0.6Zr0.4O2 catalysts obtained by the surfactant-assisted route are free of any crystalline NiO. The presence of crystalline NiO in the catalyst sample indicates that the impregnated NiO species are not homogeneously dispersed over the support surface, resulting in the formation of bulk crystalline structures. The occurrence of crystalline bulk NiO is not favorable for the dry reforming process because it is known to catalyze coke-forming reactions such as CO disproportionation and CH4 decomposition.32 The crystallite size (DXRD) of Ce0.6Zr0.4O2 in each sample was calculated by using XRD data of the most prominent lines 111, 200, 220, and 311 and is given in Table 1. In the case of the Ce/Zr supports obtained by the coprecipitation route, the average crystallite size was 4 nm, which is smaller than the average crystallite size observed in the Ce/Zr supports obtained by the surfactant-assisted route. Among the Ce/Zr supports prepared by the surfactant-assisted route, the average crystallite size decreased slightly with a decrease in the CTAB/[Ce Zr] ratio. The crystallite size of CeO2 in pristine ceria was found to be 7.2 nm. The formation of a solid solution between cerium and zirconium retards the crystallite growth, thus paving the way for the formation of thermodynamically metastable phase(s), as was observed in the previous study.47 The crystallite size of Ce0.6Zr0.4O2 in the case of nickel-impregnated catalyst samples varied in
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the range of 3.2-4.2 nm, with NCZ(0.5) exhibiting the smallest crystallite size (3.2 nm). A H2 chemisorption technique was employed to estimate the metallic surface area and metal dispersion of the active component (nickel); the observed ndings are given in Table 1. It is important to once again emphasize that all of the catalyst formulations were prepared by a standard wet impregnation method and were loaded with the same amount of nickel, i.e., 5 wt %. During a chemisorption experiment, the sample is dried, reduced in hydrogen, evacuated, then cooled to the analysis temperature (35 C), and nally evacuated before performing actual measurements. In a volumetric H2 chemisorption measurement, known amounts of hydrogen are dosed and subsequently adsorbed at dierent partial pressures, resulting in a chemisorption isotherm. This isotherm measurement is repeated after applying an evacuation step at the analysis temperature to remove weakly adsorbed species (back-sorption or a dualisotherm method). The dierence between the two isotherms represents the chemically bonded reactive gas and is used to calculate the active metal surface area. This information is combined with information on metal loading to calculate the metal dispersion. The relative measurement of chemically bound hydrogen was used to distinguish the four catalyst formulations investigated in the current study. The dispersion of nickel in the case of a coprecipitated catalyst (CZ-CP) was found to be lower than that observed in any of the surfactant-assisted catalysts and, furthermore, the nickel dispersion decreased with a decrease in the surfactant/metal molar ratio. The nickel surface area measurements also exhibit similar trends. From the above ndings, it can be inferred that a support prepared with a higher surfactant/ metal molar ratio is able to support nickel in a highly dispersed state and can also control the size of the nickel crystallites, thereby improving the nickel surface area and nickel dispersion as well as the surface nickel content. With the coprecipitated catalyst, agglomeration of nickel crystallites was conrmed from the XRD studies (Figure 2). These ndings prove that the H2 chemisorption measurements are in good agreement with the XRD results.
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Figure 3. Raman spectra of Ce0.6Zr0.4O2 supports and 5% Ni/Ce0.6Zr0.4O2 catalysts.

The Raman spectroscopic characterization was performed in order to get valuable information on both M-O (M = Ce, Zr) bond arrangement and lattice defects. In the present study, only a few representative samples, viz., CZ(0.5) and NCZ(0.5) corresponding to the lowest surfactant/metal ratio used and CZ(1.25) and NCZ(1.25) corresponding to the highest surfactant/metal ratio used, were characterized by Raman spectroscopy and are shown in Figure 3. Raman spectroscopy of all of the samples is characterized by an intense sharp Raman feature at 470 cm-1 and two broad features at 620 and 285 cm-1. The band at 470 cm-1 corresponds to the triply degenerate F2g mode and can be viewed as a symmetric breathing mode of the oxygen atoms around cerium ions.16 The weak band observed near 600 cm-1 corresponds to a nondegenerate longitudinal optical mode of CeO2, which normally should not be observed by Raman spectroscopy. Therefore, its presence may be caused by lattice defects, which lead to relaxation in the selection rules. In particular, this band has been linked to oxygen vacancies in the CeZrO2 lattice. The substitution of Zr4 ions in place of Ce4 ions causes displacement of the oxygen atoms from their ideal uorite lattice positions, resulting in the appearance of a weak band at 285 cm-1.47 The relative intensities of the band at 600 and 470 cm-1 (I600/I470) were calculated and compared in order to get a comparative estimate of the oxygen vacancy (V) concentration in the selected samples. In the case of CZ(1.25) and CZ(0.5), the ratio I600/I470 is found to be 0.25 and 0.2, respectively, while in the case of NCZ(1.25) and NCZ(0.5), it is found to be 0.625 and 0.4, respectively. From the I600/I470 values, it is clear that the V concentration is higher in the CZ(1.25) and NCZ(1.25) samples compared to the CZ(0.5) and NCZ(0.5) samples. On the basis of these results, it is established that the V concentration increases with an increase in the surfactant/metal molar ratio. Furthermore, the OSC measurements obtained by TGA also follow a similar trend; i.e., the OSC increases with and increase in the surfactant/metal molar ratio, showing that the Raman spectrocopy measurements are in agreement with the TGA measurements. The TPR proles of the support and catalyst powders obtained by surfactant-assisted and coprecipitation routes are shown in Figure 4, along with the TPR proles of pristine CeO2 and NiO. The TPR prole of pristine NiO shows a sharp feature at 440 C, which occurs due to the reduction of NiO to
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Ni. In the case of pristine CeO2, the one at the lower temperature (Tmax 600 C) was ascribed to the reduction of the surface oxygen species, and the other two broad peaks at higher temperatures (Tmax 780 and 950 C) were due to the reduction of bulk oxygen species.50 The coordinately unsaturated surface-capping oxygen ions can be easily removed in the lowtemperature region. However, bulk oxygen needs to be transported to the surface before their reduction. Consequently, the bulk reduction takes place at a higher temperature compared to the surface reduction. The bulk reduction begins only after the complete reduction of the surface-capping oxygen ions.50 Pristine ZrO2 does not show any sign of reduction below 1000 C because of its refractory nature.50 Ceria-zirconia solid solutions exhibit two distinct reduction zones; the former at lower temperatures pertains to the surface shell reduction, while the latter at higher temperatures pertains to the bulk reduction. In the case of the NCZ series of catalysts, a reduction peak at about 440-490 C is associated with the reduction of NiO to Ni and the other peaks at the higher temperature are associated with the surface and bulk reduction of Ce4 to Ce3 species. A comparison between the catalysts revealed that the catalysts whose supports were obtained by the surfactant method exhibit higher reducibility (i.e., lower Tmax) than the one obtained by coprecipitation. A comparison among the reduction proles of catalysts prepared from supports with variable CTAB/[Ce Zr] molar ratios reveal that, in the case of NCZ(0.5), the reduction of NiO occurs at higher temperatures compared to that in the case of NCZ(1.25). The TPR studies revealed that the preparation route strongly aects the reducibility of the NiO species in a given catalyst. For instance, the reduction of NiO to Ni occurs at a Tmax of 490 C in the case of the coprecipitation route and at a Tmax of 430-470 C in the case of the surfactant-assisted route. Within the family of catalysts obtained by the surfactant-assisted route, a variation in the surfactant/metal molar ratio alters the reducibility of the surface NiO species. Among them, the order of reducibility is as follows: NCZ(1.25) > NCZ(0.8) > NCZ(0.5). Reducibility is inversely proportional to the transition temperature (Tmax) of NiO to Ni species. A lower Tmax implies higher reducibility. Among the various catalysts tested in the current study, the ones obtained by the surfactant-assisted route exhibit highly complex reduction proles compared to the one obtained by the coprecipitation route. The complexity of the TPR proles is a measure of the interaction between the active component and support. XPS analysis was performed in order to understand the nature of interactions between the various surface species and to get information on their oxidation state and relative surface composition. Accordingly, the measured electron binding energies (eV) of the O 1s, Zr 3d, Ce 3d, and Ni 2p photoelectron peaks and the corresponding surface atomic composition are presented in Table 3. In the present study, only a few representative samples, viz., CZ(0.5) and NCZ(0.5) corresponding to the smallest surfactant/metal ratio used and CZ(1.25) and NCZ(1.25) corresponding to the highest surfactant/metal ratio used, were characterized by XPS. The corresponding O1s, Ce 3d, and Zr 3d peaks of the chosen samples are shown in Figure 5. It is apparent from Figure 5a that the Ce 3d spectra are complex and made up of many individual overlapping peaks. The assignment of the various peaks into two sets of spin-orbital multiplets was done by following the notation of Burroughs et al.51 In brief, the features v, v00 , v000 and u, u00 , u000 correspond to cerium in a 4 oxidation state, while the features v0, v0 and u0, u0 correspond to cerium in a
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Figure 4. TPR patterns of Ce0.6Zr0.4O2 supports and 5% Ni/Ce0.6Zr0.4O2 catalysts.

Table 3. XPS Characterization

binding energy (eV) support/catalyst Ce0.6Zr0.4O2 Ce0.6Zr0.4O2 5% Ni/Ce0.6Zr0.4O2 5% Ni/Ce0.6Zr0.4O2 CTAB/[Ce Zr] molar ratio 1.25 0.5 1.25 0.5 acronym CZ(1.25) CZ(0.5) NCZ(1.25) NCZ(0.5) O 1s 530.6 530.8 530.8 531.0 Zr 3d 182.7 182.9 182.8 183 Ce 3d 883.5 883.8 883.7 884.0 856.9 856.8 Ni 2p Zr % 59.2 62.2 55.0 60.9 surface atomic composition Ce % 40.8 37.8 31.0 32.8 14.0 6.3 Ni %

3 oxidation state. A closer look at Figure 5a reveals that the samples investigated in the current study exhibit similar types of Ce 3d XPS features. The three main features of 3d5/2 at ca. 883.5 (v), 890.0 (v00 ), and 899.5 (v000 ) and three prominent features of 3d3/2 at ca. 902.5 (u), 912.8 (u00 ), and 917.5 (u000 ) were observed, indicating the presence of cerium in a 4 oxidation state. The presence of Ce3 was established from the appearance of v0 and u0 features in the Ce 3d spectra at 887.5 and 908.5, respectively. Thus, from the above nding, it can be concluded that both the support and catalyst samples have surface cerium species in both 4 and 3 oxidation states, with the cerium(IV) species being predominant. Figure 5b shows the O 1s photoelectron peaks of selected samples. The O 1s peaks shown in Figure 4b are, in turn, composed of two peaks due to the nonequivalence of the surface oxygen chemical environments. The main feature at 530.6-531 eV corresponds to the surface lattice oxygen of a CeZrO2 solid solution, where both cerium and zirconium are present in their highest 4 oxidation state. According to the literature, the oxygen ions in pure CeO2 and ZrO2 exhibit intense peaks at 528.6-530.1 and 530.0 eV, respectively.47 The broad feature (indicated by the blue circle) in Figure 5b corresponds to the oxide ions bonded to cerium(III) species, which are formed as a result of oxygen vacancy formation (which helps to maintain the charge neutrality), and as a result, an additional O 1s peak at the higher BE end (2.0-2.2 eV) is formed.52 Figure 5c shows the Zr 3d photoelectron peaks of selected samples investigated in the current study. The corresponding BE values are shown in Table 3. As can be noted from Table 3, the BE values are in the range of 182.7-183.0 eV, which agrees well with earlier literature reports and corresponds to
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zirconium in a 4 oxidation state.53 Galtayries et al.,54 who studied ceria-zirconia solid solutions of varying composition, reported a BE of Zr 3d5/2 of 181.7-181.8 eV. The Ni 2p3/2 peak (850-870 eV), not shown here, was used for chemical state identication and quantication purposes. In the case of NCZ(1.25) and NCZ(0.5), the Ni 2p3/2 peak BE values were recorded at 856.9 and 856.8 eV, respectively. The above observed BE values agree well with those reported for NiO and Ni(NO3)2, where Ni is present in its most stable oxidation state, i.e., nickel(II).55 On the whole, the XPS studies revealed the presence of nickel and zirconium in their highest oxidation states, i.e., nickel(II) and zirconium(IV), respectively, while cerium was found to exist in both 4 and 3 oxidation states. The surface atomic compositions of the selected supports and catalysts, as determined by XPS, are presented in Table 3. The trends observed in Table 3 provide valuable information on the nature of the surface-active sites, which is vital for explaining their resultant catalytic activities. From Table 3, it is evident that the surface atomic composition varied with a variation of the surfactant/metal molar ratio. The surface of NCZ(1.25) was composed of 31.0% surface cerium and 14% surface nickel species, while the surface of NCZ(0.5) had 32.8% surface cerium and 6.3% surface nickel species. The marked superior performance of NCZ(1.25) over that of NCZ(0.5) for a CO2 reforming reaction can therefore be partly attributed to their surface atomic composition. From the current observation, it is apparent that a higher surface nickel content (active component) and/or a lower surface cerium content (redox component), either individually or combined, is/are necessary to obtain a superior catalyst formulation. The bulk enrichment of cerium helps to promote
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Figure 5. XPS spectra of Ce0.6Zr0.4O2 supports and 5% Ni/Ce0.6Zr0.4O2 catalysts.

the oxygen transport/buer capacity of the catalyst.48 From the current results, it seems that there is a correlation between the amount of surfactant employed and the degree of nickel dispersion. With an increase in the amount of surfactant employed, it is possible to improve the dispersion of nickel over the support surface. The above ndings on the surface atomic composition of nickel agree well with the H2 chemisorption measurements, presented earlier in Table 1. 3.2. Catalyst Performance Evaluation. 3.2.1. Effect of the Preparation Method and CTAB/[Ce Zr] Molar Ratio on the Catalyst Performance for CO2 Reforming of CH4. All of the catalytic tests were performed under identical operating conditions. The performance of the different catalyst formulations was measured in terms of the activity and stability. The tests were performed at 800 C using feed composed of 1:1:0.5 (vol %) CH4/CO2/N2 at a flow rate of 100 sscm; the results obtained thereof are presented in Figure 6. The direct measurement of the textural and thermal stability of any given catalyst is its catalytic activity and stability. From Figure 6, it is found that the catalysts obtained by the surfactant-assisted route exhibit high initial activity with reasonable stability for the given time on stream (TOS) of operation. The initial activity of the coprecipitated catalyst was similar to that of the catalysts obtained by the surfactant-assisted route. However, the activity of the coprecipitated catalyst started to deteriorate from 1 h TOS, losing 12% activity (% CH4 conversion) in the first 8 h. A comparison of the activity data of catalysts prepared with different surfactant/metal molar ratios indicates that the amount of surfactant employed plays a significant role in the resultant activity and stability, and only NCZ(1.25) and NCZ(0.8) catalysts deliver a stable performance. All of the catalysts prepared in the current study exhibit almost similar initial catalytic activity in terms of CH4 conversion (Figure 6; % CH4 conversion, 1 h data). However, beyond that, their relative catalytic activities vary significantly. The reason behind the identical initial activity can be explained in terms of nickel loading (active component) and its rate of sintering and agglomeration. Because all of the Ce0.6Zr0.4O2 supports prepared in the current work were impregnated with a nominal amount of 5 wt % Ni under exactly identical conditions, all of the fresh catalysts would exhibit almost identical initial responses to the CH4/CO2 feed. However, with time, the one obtained by the coprecipitation route seems to deactivate faster because of coke
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deposition, thereby leading to a decline in the activity. On the other hand, the catalysts obtained by the surfactant-assisted route, followed by considerable (5 days) hydrothermal aging, maintain a steady active site density over the surface of the catalyst. This reasoning is supported by the XRD studies (Figure 2) performed on the fresh catalyst samples, which reveal the existence of crystalline NiO in the sample obtained by the coprecipitation route and the nonexistence of any crystalline NiO in the case of catalysts obtained by the surfactant-assisted route. The crystalline NiO (large ensembles) is known to catalyze coke formation reactions, while the nickel present in a highly dispersed state is found to be beneficial for the dry reforming of methane.56 The overall results show that a high dispersion of NiO leads to better stability, as noted in Figure 6. On the whole, from the current study, it can be inferred that the use of a high surfactant/metal molar ratio led to better dispersion of the NiO species, as noted from the H2 chemisorption studies; thus, a stable catalyst formulation [NCZ(1.25)] for the dry reforming of methane is formed. Figure 6 also shows activity variations with TOS in terms of the TOF of CH4 observed for the investigated catalysts. In the present study, it is noted that the catalyst formulation [NCZ(1.25)] that exhibits the highest CH4 conversion has the most surface nickel (Table 1) but possesses the lowest TOF for methane. From the above results, it can be hypothesized that not all of the surface nickel sites present in the NCZ(1.25) formulation participate in the dry reforming process. According to the literature, both the surface-active metal sites and lattice oxygen defects (oxygen vacancies) have to be present in the right proportion for the nickel site to participate eectively in the dry reforming reaction.57 Numerical analysis of the surface nickel sites and oxygen vacancies was performed for all of the catalyst formulations used in this study. It can be considered that (i) the atomic cross section of each nickel atom is about 6.49 2 (1 2 = 10-20 m2), (ii) the density of nickel metal is 8.91 g cm-3, and (iii) nickel can be assumed to be present in the face-centeredcubic lattice. According to the spherical model for the metallic particles, the NCZ(1.25) catalyst having a nickel surface area of 2.45 m2 (g of cat.)-1 will have 3.77 1019 nickel atoms per gram of catalyst. With similar calculations, the NCZ(0.8), NCZ(0.5), and NCZ(CP) catalysts will have 3.06 1019, 2.74 1019, and 2.14 1019 nickel atoms per gram of catalyst, respectively.
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Figure 6. Performance evaluation of 5% Ni/Ce0.6Zr0.4O2 catalysts for a typical CO2 (dry) reforming reaction [feed composition (vol %) CH4/CO2/N2 = 40/40/20; temperature = 800 C; feed ow rate = 100 sccm].

From the OSC measurements, the estimated numbers of oxygen vacancies in the NCZ(1.25), NCZ(0.8), NCZ(0.5), and NCZ(CP) catalyst formulations are 6.58 1020, 6.21 1020, 5.64 1020, and 5.21 1020 oxygen vacancies per gram catalyst, respectively. By following the measurements of surfaceactive nickel sites and oxygen vacancy defects, it is clear that, among all of the catalyst formulations, NCZ(1.25) possesses the largest number of both surface-active nickel sites and oxygen vacancies. However, it is observed from the TOF results that it is the ratio of the total number of oxygen vacancies per gram of catalyst to the total number of surface nickel atoms per gram of catalyst that is related to the observed initial TOF of CH4 (1 h data). As this ratio increases, the initial TOF of CH4 also increases, as shown in Figure 7. Thus, these observations conrm that both the surface-active metal sites and lattice oxygen defects (oxygen vacancies) have to be present in the right proportion for each nickel site to participate eectively in the dry reforming reaction.57 3.2.2. Effect of the Addition of Steam on the Performance of Catalysts for CO2 Reforming of CH4. Li et al.45 reported that the addition of steam to the dry reforming feed gas (mixed reforming) can significantly minimize catalyst deactivation caused by coke deposition on the catalyst surface. The steam/methane ratio plays an important role in the overall steam-assisted dry reforming process. Generally, higher steam/methane ratios yield higher conversions, but excess steam over that required by the reaction stoichiometry is energetically unfavorable and also dilutes the feed gas. On the contrary, the use of lower steam/methane ratios leads to carbon deposition problems.37 In order to find out whether the addition of steam is beneficial to the overall activity, two catalyst formulations, namely, NCZ(1.25) and NCZ(0.5), were screened under identical operating conditions with H2O/ CH4 = 1, CH4/CO2 = 1, T = 800 C, flow = 100 sscm, and feed ratio H2O/CH4/CO2/N2 = 1/1/1/0.5 vol %. The results obtained are shown in Figure 8. The addition of a stoichiometric amount of steam to the CO2 reforming feed gas mixture resulted in a decrease in CH4 conversion and led to catalyst deactivation. Steam addition increases the surface coverage by oxygen and, hence, surface nickel atoms are partly oxidized. Stabilization of nickel cations by the support decreases the number of accessible active nickel atoms. This explains the decline of activity. The CO2 reforming reaction was predominant under the experimental conditions employed in the current study, while the steam reforming reaction was negligible. The above observation is confirmed by the obtained H2/CO ratios, which were 1. Thus, the obtained results indicate a poor performance of the above-tested catalysts for the CO2 reforming of CH4 reaction
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Figure 7. Plot showing the relationship between the initial TOF of CH4 and the ratio of oxygen vacancies/surface nickel atoms.

in the presence of steam. The above results can be explained from the perspective of hydrophilicity. According to Gonzleza Velascos findings,58 hydrophilicity is introduced into the ceria system upon the addition of zirconium, which increases with an increase in the zirconium content. The inherently hydrophilic ceria-zirconia-based catalysts strongly adsorb water, thereby blocking the catalyst active sites (inhibition of active sites by water) and causing catalyst deactivation. The higher ionic character of the Zr-O bond compared to that of the Ce-O bond promotes the hydrophilic character of the Ce0.6Zr0.4O2 surface, making surface rehydroxylation an easy process in the presence of steam. It is important to mention that all 5% Ni/ Ce0.6Zr0.4O2 catalysts prepared by the surfactant-assisted route perform well in a CO2 reforming reaction but are prone to deactivation in the presence of steam. Further studies are needed to understand the complete surface chemistry and the aspects responsible for the observed deactivation in the presence of steam. 3.2.3. Effect of the Temperature on the Catalytic Activity for CO2 Reforming of CH4. From the above tests, it is clear that the addition of steam to the dry reforming reaction is not beneficial with the 5% Ni/Ce0.6Zr0.4O2 catalysts obtained by the surfactantassisted route. In order to achieve one of the set goals of the current study, the dry reforming reaction was performed at lower operating temperature, i.e., 700 C, over catalysts obtained by the surfactant-assisted route. The results thus obtained are compared in Figure 9. The figure reveals a lower catalytic activity at lower operating temperature because of the endothermic nature of the reaction. On the whole, the performances of both NCZ(1.25)
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Figure 8. Screening of 5% Ni/Ce0.6Zr0.4O2 catalysts for the CO2 reforming reaction in the presence of steam [feed composition (vol %) H2O/CH4/ CO2/N2 = 40/40/40/20; temperature = 800 C; feed ow rate = 140 sccm].

Figure 9. Inuence of the temperature on the catalytic activity of 5% Ni/Ce0.6Zr0.4O2 catalyst for CO2 reforming of CH4 [feed composition (vol %) CH4/CO2/N2 = 40/40/20; feed ow rate = 100 sccm; temperatures = 700 and 800 C].

and NCZ(0.5) catalysts are found to be stable even at 700 C operating temperature. On the basis of these results, it appears that it is possible to employ 5% Ni/Ce0.6Zr0.4O2 catalysts obtained by the surfactant-assisted route even at an operating temperature as low as 700 C for the dry reforming reaction. 3.3. SARs. The performance evaluation results (Figure 6) show a marked difference in terms of activity and stability between the catalysts where the supports are prepared through the surfactant-assisted method and the other one is prepared by coprecipitation. It also shows a marked difference in the activity and stability between the catalysts prepared by the surfactantassisted method but using different CTAB/(Ce Zr) ratios. It is a well-known fact in the literature that the synthesis and preparation conditions affect some properties of ceria-based materials such as the formed phase, particle size, surface area, and OSC, which, in turn, influence the resultant catalytic activities. The enhancement of the surface area of ceriazirconia-based solid solutions prepared by the surfactant-assisted route is related to the surfactant effect that reduces the surface tension inside the pores through a decrease in the capillary stress during drying and calcination processes. Better thermal stability of the above-obtained materials is related to the structural
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arrangement and morphology of the inorganic-organic composites, which are produced by an exchange between the deprotonated hydroxyl group of the oxides and the alkylammonium cations. These features contribute to the enhanced textural stability of the catalysts obtained by the surfactant-assisted route in comparison with the one prepared by the conventional precipitation method. We have used the characterization results in conjunction with the activity results in an attempt to establish SARs for each catalyst system. Figure 10 represents the various SAR plots generated in this study. Certain parameters, namely, (1) OSC, (2) reducibility, and (3) nickel surface area, were used to establish the SARs. The OSC measurements were obtained from TGA under cyclic reductive/oxidative excursions, as described earlier (Table 1). The reducibility values were obtained from the TPR measurements (Figure 4); more specically, the Tmax values pertaining to the reduction of NiO to Ni were used for calculation of the reducibility (where reducibility = 1/Tmax 100). The nickel surface area measurements were obtained from H2 chemisorption experiments (Table 1). In the current work, the activity is dened in terms of % CH4 conversion observed at 8 h of TOS.
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Figure 11. Long-term TOS stability studies on the 5% Ni/Ce0.6Zr0.4O2-NCZ(1.25) catalyst [feed composition (vol %) CH4/CO2/N2 = 40/40/20; temperature = 800 C; feed ow rate = 100 sccm].

Figure 10. Structure-activity correlation plots for CO2 reforming of CH4: (A) activity vs OSC; (B) activity vs reducibility; (C) activity vs nickel surface area.

Figure 10A represents the correlation plot of activity with OSC. As is evident from Figure 10A, an increase in OSC leads to an improvement in the resultant catalytic activity. As mentioned earlier, the OSC of a catalyst is its ability to transition between the reduced and oxidized states rapidly. The magnitude of the OSC denotes the ease of occurrence of the Ce4 S Ce3 redox couple, which is known to promote CO2 reforming processes and also assist in the decoking of the catalyst surface. The relationship between the activity and catalyst reducibility is presented in Figure 10B. The higher the reducibility, the lower is its reduction temperature (Tmax). The descending order of reducibility observed for the various catalysts tested in the current study is as follows: NCZ(1.25) > NCZ(0.8) > NCZ(0.5) > NCZ(CP). The trends show a somewhat monotonic increase in the relationship between the reducibility and activity, which means that highly reducible catalysts exhibit enhanced stability
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and high activity. The correlation between the catalyst stability and nickel surface area is presented in Figure 10C. It is noted from this gure that the catalyst activity improves with an increase in the nickel surface area. The catalyst that possesses a greater nickel surface area and a greater proportion of surface nickel compared to bulk nickel will exhibit longer life for the CO2 reforming reaction. Out of the four catalyst formulations tested in the current work, only NCZ(1.25) and NCZ(0.8) obtained by the surfactant-assisted route exhibit steady and highest catalytic activity, while the other two, namely, NCZ(0.5) and NCZ, are not stable and their catalytic activity decays with TOS. On the basis of the current ndings, it can be inferred that the surfactant-assisted route yields better catalyst formulations compared to the conventional coprecipitation route. Also, among the catalysts obtained by the surfactantassisted route, the amount of surfactant used during the course of the support preparation plays a pivotal role in imparting the desired characteristics to the resultant catalyst formulation. From the current study, it can be inferred that, in order to obtain a better catalyst formulation, the optimum molar ratio of CTAB/[Ce Zr] should be g0.8. Before this discussion is concluded, it is very important to mention here that, although there were many concrete correlations between the observed catalytic activity/stability and textural/physicochemical characteristics, it would be best to consider that the right combination of all relevant characteristics is responsible for the resultant overall activity and that the percentage contribution from each characteristic to the overall activity is not necessarily the same. On the basis of our studies, it was noted that the absence of any desired characteristic in a given catalyst formulation leads to a poor performance or even deactivation. From the present investigation, it is quite apparent that high OSC, high surface area, high reducibility, high nickel surface area, high nickel dispersion, and high surface nickel content lead to excellent catalytic activity for CO2 reforming of CH4. Among the various catalyst formulations investigated in the current study, the catalyst NCZ(1.25) has all of the desirable characteristics and subsequently exhibits superior catalytic activity along with enhanced stability, as is established by a long-term stability run for a duration of 150 h, as is shown in Figure 11.32 Thus, there is an
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4. CONCLUSIONS 1 The results showed a marked dierence in the activity and stability between the catalysts where the supports were prepared by surfactant-assisted route and the other one was prepared by coprecipitation. It also showed a marked dierence in the activity and stability between the catalysts prepared by the surfactant-assisted route but using dierent CTAB/(Ce Zr) molar ratios. Also, the use of steam to assist the dry reforming process produced dierences in terms of the activity and stability. 2 The surfactant-assisted route yields better catalysts than the conventional coprecipitation route. 3 Within the range of CTAB/[Ce Zr] molar ratios employed, the amount of surfactant used during the course of the support preparation aects the stability, with catalysts prepared by a higher surfactant/metal molar ratio exhibiting better stability. 4 From structure-activity correlation (SAR) plots, it is noted that the higher the OSC, surface area, nickel surface area, nickel dispersion, reducibility, and surface nickel content, the higher is the CH4 conversion and stability for the CO2 reforming of CH4 reaction. 5 The initial TOF of CH4 increases as the ratio of the total number of oxygen vacancies per gram of catalyst to the total number of surface nickel atoms per gram of catalyst increases. 6 The catalysts obtained by the surfactant-assisted route fare extremely well in a CO2 reforming process but are prone to deactivation in the presence of steam. The inherent hydrophilic nature of the ceria-zirconia support oered reduced sensitivity to water inhibition of active sites, leading to catalyst deactivation.
AUTHOR INFORMATION
Corresponding Author

*E-mail: Raphael.idem@uregina.ca.

ACKNOWLEDGMENT The nancial support provided by the Natural Sciences and Engineering Research Council of Canada is gratefully acknowledged. REFERENCES
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