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Applied Catalysis B: Environmental 102 (2011) 291301

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Applied Catalysis B: Environmental


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Surface reactivity of LaCoO3 and Ru/LaCoO3 towards CO, CO2 and C3 H8 : Effect of H2 and O2 pretreatments
M. Consuelo lvarez-Galvn a , Domna A. Constantinou b , Runo M. Navarro a , Jos A. Villoria a , Jos Luis G. Fierro a , Angelos M. Efstathiou b,
a b

Instituto de Catlisis y Petroleoqumica, CSIC, C/Marie Curie 2, Cantoblanco, 28049, Madrid, Spain Department of Chemistry, Heterogeneous Catalysis Laboratory, University of Cyprus, P.O. Box 20537, CY 1678 Nicosia, Cyprus

a r t i c l e

i n f o

a b s t r a c t
The differences in surface reactivity of LaCoO3 and Ru/LaCoO3 solids after pre-treatment in a hydrogen or oxygen gas atmosphere towards oxidative steam reforming (OSR) of propane was probed by performing temperature-programmed desorption (TPD) of CO and CO2 , temperature-programmed surface reaction (TPSR) of C3 H8 , transient isothermal oxidation of carbon formed after TPSR of C3 H8 , X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) studies. The TPD of CO and CO2 studies revealed a greater adsorption of these molecular product species of the OSR of propane on the surface of LaCoO3 than Ru/LaCoO3 solid, while XPS studies performed after reduction in hydrogen revealed a higher concentration of Co2+ in the LaCoO3 than Ru/LaCoO3 solid catalyst composition. The Ru/LaCoO3 solid was found to exhibit after an induction period enhanced reactivity towards H2 production for the OSR of propane reaction compared to LaCoO3 after hydrogen reduction at 750 C. These results led to the conclusion that the introduction of a small amount of Ru (0.8 wt%) on lanthanum cobaltite surface leads to a higher concentration of metallic cobalt (Co0 ) after hydrogen reduction is performed, thus favouring the enhancement of necessary active catalytic sites on the Co, LaCoO3 and La2 O3 surfaces formed. TPSR of propane used as model compound of diesel revealed the participation of surface lattice oxygen of both LaCoO3 and Ru/LaCoO3 pre-oxidized solids as well as the formation of hydrogen by reaction of propane on the Co0 (metallic state) surface once the latter is formed. A greater reactivity of propane during TPSR was observed over the Ru/LaCoO3 solid surface for either oxidative or reductive pre-treatments. Also, a lower amount (2.13 mmol/g) of carbon deposition was found on Ru/LaCoO3 compared to LaCoO3 (3.65 mmol/g) at the end of the TPSR of propane experiment. These results provide important fundamental information on the role of Ru in the Ru/LaCoO3 system towards catalytic oxidative steam reforming of propane. 2010 Elsevier B.V. All rights reserved.

Article history: Received 17 September 2010 Received in revised form 5 December 2010 Accepted 8 December 2010 Available online 16 December 2010 Keywords: Oxidative steam reforming of propane H2 production LaCoO3 Ru Perovskite CO-TPD CO2 -TPD Propane TPSR

1. Introduction Nowadays, the use of hydrogen as an energy carrier in fuel cells is receiving considerable attention due to environmental concerns and to the higher efciency of these systems compared to internal combustion engines [1]. Widely available logistic fuels (e.g., diesel) with a high volumetric energy density can be readily reformed into a hydrogen-rich gas and directly be applied in fuel cells [2]. The production of molecular hydrogen using diesel hydrocarbon compounds can be achieved by different catalytic processes such as partial oxidation (POX), steam reforming (SR) or oxidative steam reforming (OSR) [3]. The latter process is more efcient due to the in situ integration of the reaction heat of the exothermic

Corresponding author. Tel.: +35722 892776; fax: +357 22 892801. E-mail address: efstath@ucy.ac.cy (A.M. Efstathiou). 0926-3373/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.apcatb.2010.12.015

partial oxidation into the steam reforming endothermic reaction [1,4,5]. The oxidative steam reforming reaction can be performed at high reaction temperatures (800900 C) in the presence of an active and stable catalyst having a good resistance to coking and sulphur poisoning [6]. The dispersion of a metal throughout the structure of a stable metal oxide could maximize the active phase exposition and reduce the possibility of large metal clusters formation that are potential sites for sulphur and carbon accumulation, and as a result of this, catalysts less susceptible to deactivation have been developed [7,8]. Mixed metal oxides including perovskites (ABO3 ) are becoming increasingly attractive as catalyst precursors for oxidative steam reforming reactions due to their ability to generate a good dispersion of the active phase B in metallic state (B0 ) over a matrix of the oxide A and be stable in the highly reductive gas atmosphere at the reaction conditions used [9,10]. In addition, it has been reported [11,12] that the use of a transition metal

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such as La in the A position of a perovskite (ABO3 ) structure can be a good metal candidate since it leads to the formation of lanthanum oxycarbonate under reaction conditions which was found to participate in the reduction of carbon deposition via gasication. Moreover, the high interaction between both metallic cobalt and lanthana phases derived by reduction of the perovskite structure produces a synergy which promotes the formation of syngas [10]. The incorporation of small amounts (ca. less than 1 wt%) of transition metals, like ruthenium (Ru) has been found to result in the increase of catalytic activity and stability for the oxidative steam reforming of heavy hydrocarbons towards hydrogen production not only by the higher intrinsic activity of this metal, but also because small proportion of ruthenium promotes the reduction of the system, thus increasing the surface proportion of active phases [10]. Liu and Krumpelt [13] found that the incorporation of Ru into a perovskite type structure (LaCr0.95 Ru0.05 O3 ) led to a catalytically active system for the autothermal reforming of n-dodecane into hydrogen having good resistance to sulphur deposition. Also, Navarro et al. [10] have reported an increased efciency in hydrogen production during oxidative steam reforming of diesel over a Ru/LaCoO3 catalyst (0.02:1:1 molar, Ru/Co/La) compared to Ce and/or La alumina-doped supported Pt or Ni catalysts. Different reactions are involved in the oxidative steam reforming of diesel such as partial oxidation, steam reforming, total oxidation and watergas shift (WGS), all of them resulting to H2 , CO and CO2 reaction products [14,15]. Thus, understanding the interactions of H2 , CO and CO2 with the surface of ABO3 and Ru/ABO3 solids mentioned above is essential for establishing relationships of their catalytic performance with physicochemical properties. According to the above mentioned, the present study provides for the rst time fundamental information on the CO and CO2 chemisorptive behaviour of LaCoO3 and Ru/LaCoO3 solids via temperature-programmed desorption experiments (CO-TPD and CO2 -TPD) for different hydrogen or oxygen gas pre-treatment conditions applied on the solids. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) studies have also been conducted for additional surface characterization of the catalytic systems investigated (e.g., crystal phases, primary crystal size, surface atom% composition, extent of cobalt reduction following H2 pre-treatment of the solids). Propane is derived via the homolytic cracking of hydrocarbon molecules present in diesel [16]. In a blank experiment performed in the present work in the absence of a catalyst, it was found that after passing vaporized diesel in the reactor propane was the hydrocarbon formed with the highest concentration in the product stream for the reaction conditions (T, GHSV) used in this study. Therefore, propane has been used as a model hydrocarbon present in a catalytic reactor during oxidative steam reforming of diesel. For this, temperature-programmed surface reaction (TPSR) studies using propane were performed after different reductive or oxidative pre-treatments of the LaCoO3 and Ru/LaCoO3 solids were made in order to probe the participation of lattice oxygen during propane oxidative steam reforming and to characterize the carbon formed.

quently, an excess (10 vol%) of the required aqueous solution of K2 CO3 (>99.0%, Johnson Matthey) was rapidly added. Under the prevailed basic conditions (pH > 9), water was partially evaporated by heating the solution to 70 C. Before ltering, the precipitate was washed with ice-cooled distilled water until the pH of the ltrate became neutral. The solid precursors thus obtained were then dried at 110 C for 4 h and calcined in air (static conditions) at 750 C for 4 h (heating rate used was 3 C/min from 110 to 750 C). The Ru/LaCoO3 solid was prepared by the wet impregnation method using an appropriate amount of RuCl3 (ruthenium chloride, 48.91% Ru, Premion, Johnson Matthey) in order to achieve a Ru:La:Co = 0.02:1:1 molar ratio. Impregnation was carried out in a rotary evaporator at 80 C for 2 h. Finally, the samples were dried at 110 C for 4 h and then calcined in air (static conditions) at 500 C for 3 h. 2.2. Catalysts characterization studies 2.2.1. X-ray diffraction (XRD) X-ray diffraction (XRD) patterns were recorded using a Seifert 3000P vertical diffractometer and nickel-ltered CuK radiation ( = 0.1538 nm). The mean particle size of LaCoO3 in the calcined (static air, 750 C, 4 h) samples, and of the Co0 , La2 O3 and La(OH)3 obtained after hydrogen reduction of the samples (10 vol% H2 /N2 gas mixture, 750 C, 2 h) was estimated using the Scherrer equation [17]; the width of XRD peak was considered as the full-width at half maximum intensity of the most intense and least overlapped peak (2 = 47.7 for LaCoO3 ; 44.3 for Co0 ; 30.0 for La2 O3 ; 48.6 for La(OH)3 )). The samples for analysis were reduced ex-situ and transferred in the XRD instrument in a vial containing iso-octane to avoid oxidation. Hydrogen-containing gas was passed through the reactor when the sample was transferred in the vial. 2.2.2. X-ray photoelectron spectroscopy (XPS) X-ray photoelectron spectroscopy measurements were performed using an Escalab 200R spectrometer equipped with a hemispherical electron analyser and an Al K (h = 1486.6, 120 W) X-ray source. The area of a given peak was estimated by calculating the integral of it after smoothing and subtracting an S-shaped background, while tting of the thus derived experimental spectrum was made using a mixture of Lorentzian and Gaussian lines of variable proportions. All binding energies (BE) were referenced to the C 1s signal at 284.6 eV based on carbon contamination of the sample. Quantication of the surface atomic composition was obtained after integration of the peaks and using appropriate corrections for sensitivity factors [18]. XPS analyses on the LaCoO3 and Ru/LaCoO3 solids were performed following in situ reduction of the solid in the pre-treatment chamber of the XPS apparatus. 2.2.3. Temperature-programmed desorption (TPD) All TPD runs (H2 -TPD, CO-TPD and CO2 -TPD) were conducted in a specially designed gas-ow system described previously [19] and after using a 0.5 g catalyst sample, 30 NmL min1 He ow, and 30 C min1 heating rate. Quantitative analysis of the efuent gas stream from the micro-reactor was done with an on line quadrupole mass spectrometer (MS) (Omnistar, Balzers) equipped with a fast response inlet capillary/leak valve (SVI050, Balzers) and data acquisition systems [19]. The mass numbers (m/z) 2, 28 and 44 used for H2 , CO and CO2 , respectively, were continuously recorded. Calibration of H2 , CO and CO2 signals of the mass spectrometer was made based on certied 1 vol% H2 , 1 vol% CO and 1.0 vol% CO2 in He diluent gas mixtures. For the quantitative analysis of a gas mixture containing both CO and CO2 , the contribution of CO2 to the m/z = 28 MS signal was considered.

2. Experimental 2.1. Synthesis of catalysts LaCoO3 perovskite was prepared by simultaneous precipitation of cobalt and lanthanum from a solution of nitrate salts of cobalt and lanthanum after using K2 CO3 as a precipitating agent. More precisely, the required amount of La(NO3 )3 6H2 O (99.9%, Johnson Matthey) or Co(NO3 )2 6H2 O (97.7% minimum, Johnson Matthey) salt was dissolved in distilled water in order to obtain a 1 M solution. Both solutions were then mixed under vigorous stirring. Subse-

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2.2.4. Metal dispersion measurements (H2 -TPD) The dispersion of cobalt and ruthenium/cobalt metals in the LaCoO3 and Ru/LaCoO3 catalysts, respectively, was determined by selective H2 chemisorption at 25 C followed by TPD in He ow according to the following procedure. The fresh catalyst sample (as prepared, Section 2.1) was rst heated in He ow to 750 C and then reduced in a 10 vol% H2 /He gas mixture at 750 C for 2 h. Following reduction, the feed was changed to He and the temperature was decreased to 100 C in He ow. The feed was then changed to a 1 vol% H2 /He gas mixture for 30 min. After this adsorption step the catalyst was cooled in 1 vol% H2 /He to room temperature and left for 15 min. A switch to He ow was then made for 15 min until no H2 signal could be observed in the mass spectrometer, and the temperature of the catalyst was then increased to 700 C at the rate of 30 C/min in order to carry out a TPD run. Integration of the H2 -TPD response curve obtained and considering the amount of cobalt or the ruthenium/cobalt in the respective catalyst sample, the metal dispersion was estimated.

2.4. Estimation of carbon deposition under TPSR in C3 H8 /He ow The amount of carbonaceous species accumulated on the surface of the investigated solid catalysts following TPSR of C3 H8 (Section 2.3), where the solids were rst oxidized at 600 C for 2 h (Section 2.3) was measured as follows. At the end of TPSR run (700 C) the feed was changed to He until all MS signals, and in particular the CO (m/z = 28) and CO2 (m/z = 44) reached their respective baseline value. Then, the catalyst sample was cooled to 600 C in He ow. The gas-ow was then switched to 2 vol% O2 /He gas mixture at 600 C, and the signals of CO and CO2 were continuously monitored by on line mass spectrometer. The amount of surface carbon deposits (g C/g catalyst) was calculated based on the CO and CO2 response curves calibrated against standard 1 vol% CO and 1 vol% CO2 gas mixtures in He diluent. 2.5. Catalytic oxidative steam reforming of propane Catalytic activity performance tests of the investigated catalyst samples (Section 2.1) towards oxidative steam reforming of propane for hydrogen production were carried out in a xed-bed continuous ow stainless steel micro-reactor. The LaCoO3 -based solid catalyst samples were reduced in 10 vol% H2 N2 gas mixture at 750 C for 2 h before activity tests. The ow rates of the propane and liquid water feed streams were controlled by mass ow controller and liquid pump, respectively. The liquid feed was pre-heated to 200 C in an evaporator before entering the catalyst bed. Nitrogen gas (25 NmL/min) was also fed into the evaporator in order to facilitate evaporation of water and gas mixing. The resulting gas mixture was mixed with an appropriate oxygen ow before entering the catalytic reactor at a molar ratio of H2 O/O2 /C = 3/0.5/1, whereas the total pressure was close to 1 atm and the total gas ow rate was 75 NmL/min (GHSV = 20,000 h1 ). Catalyst activity in terms of H2 -yield (%) was measured at 750 C. The reaction products were analysed by on line gas chromatograph (HP 5890 Series II) equipped with a thermal conductivity detector. 3. Results and discussion 3.1. Catalysts characterization 3.1.1. XRD analyses The XRD patterns of the pre-calcined LaCoO3 and Ru/LaCoO3 samples shown in Fig. 1 were found to be similar to those previously reported [10], having strong reections at 32.9 (1 1 0) and 33.3 (1 0 4) which correspond to stoichiometric perovskite with a

2.2.5. CO Temperature-programmed desorption (CO-TPD) CO-TPD experiments were performed following chemisorption from a 2 vol% CO/He gas mixture at room temperature for 30 min. Before CO chemisorption the fresh sample of LaCoO3 or Ru/LaCoO3 (as prepared, Section 2.1) was reduced in a 10% H2 /He gas mixture at 750 C for 2 h and then brought quickly in He ow to room temperature. Following CO chemisorption the catalyst sample was purged in He ow at room temperature until no CO evolution was observed. CO-TPD runs were conducted in the 25700 C range.

2.2.6. CO2 Temperature-programmed desorption (CO2 -TPD) CO2 -TPD experiments were performed following chemisorption of CO2 at 25 C from a 3 vol% CO2 /He gas mixture for 30 min. The fresh catalyst sample was rst reduced in 10 vol% H2 /He at 300, 500 or 750 C for 2 h. This different hydrogen reduction treatment was performed in order to investigate the effect of oxygen vacant site concentration formed on the surface of LaCoO3 and Ru/LaCoO3 solids by hydrogen reduction on the chemisorptive behaviour of CO2 . The temperature of the catalyst was then increased from room temperature to 700 C to carry out a TPD run.

2.3. Temperature-programmed surface reaction (TPSR) of C3 H8 TPSR of C3 H8 experiments were conducted in a specially designed gas-ow system previously described [19]. The reactant propane (C3 H8 ) and the H2 , CH4 , H2 O, CO and CO2 gas products were monitored by on line quadrupole mass spectrometer (MS) at the m/z = 43, 2, 16, 18, 28, and 44, respectively. It is mentioned here that propane leads to m/z = 28, 43 and 44 signals in the ionization chamber of the mass spectrometer. In addition, the signal at m/z = 28 also arises from CO and CO2 (formation of CO+ in the ionization chamber of MS). Therefore, the signal recorded at m/z = 43 was derived exclusively from the propane molecule. In order to investigate the inuence of the extent of reduction or oxidation of LaCoO3 perovskite structure on the TPSR of propane traces, three different gas pre-treatment conditions were used: (a) hydrogen reduction at 750 C for 2 h in a 10 vol% H2 /He gas mixture, (b) oxidation at 400 C for 2 h in a 10 vol% O2 /He gas mixture, and (c) oxidation at 600 C for 2 h in a 10 vol% O2 /He gas mixture. After the above described solid pre-treatment, the solid catalyst (0.5 g) was cooled to room temperature in He ow. The feed was subsequently switched to a 2 vol% C3 H8 /He gas mixture and at the same time the temperature of the solid was increased to 700 C at the rate of 30 C/min.

R. Rhombohedral
R R R R R R R R R R

Ru/LaCoO 3

I/Io (a.u.)

R R

LaCoO3
R R

10

20

30

40

50

60

70

80

2 ()
Fig. 1. XRD patterns of pre-calcined LaCoO3 and Ru/LaCoO3 perovskites (see Section 2.2.1).

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Table 1 Average primary crystal size (nm) of LaCoO3 , Co0 , La2 O3 and La(OH)3 solids for the fresh (as prepared, Section 2.1), calcined, and reduced LaCoO3 and Ru/LaCoO3 solids calculated using the Scherrer equation. Fresh samples LaCoO3 Calcined T = 750 C/4 h Reduced T = 750 C/2 h LaCoO3 44.2 La2 O3 La(OH)3 31.8 13.1 Ru/LaCoO3 LaCoO3 42.1 La2 O3 La(OH)3 30.6 11.7

Co0 35.0

Co0 28.6

Counts per second (a.u.)

rhombohedral distortion (JCPDS 48-123) of the ideal cubic structure of perovskite. No segregated phases corresponding to La or Co oxides were detected. Estimation of the mean primary LaCoO3 crystallite size using the Scherrer equation [17] led to a slightly smaller crystallite size for the Ru/LaCoO3 compared to LaCoO3 solid (Table 1). The XRD patterns of the reduced at 750 C/2 h LaCoO3 and Ru/LaCoO3 samples are presented in Fig. 2. After comparing the diffractograms recorded for the calcined samples with those obtained after reduction (Figs. 1 and 2), it is concluded that the diffraction peaks corresponding to LaCoO3 were replaced by 2diffraction peaks attributed to La2 O3 (JCPDS 74-2430), La(OH)3 (JCPDS 006-585) and Co0 (JCPDS 15-806). The mean primary crystal sizes of Co0 , La2 O3 and La(OH)3 solids derived from the reduced Ru/LaCoO3 solid formulation were found to be smaller than those obtained for the reduced LaCoO3 solid as reported in Table 1. 3.1.2. XPS studies X-ray photoelectron spectroscopy was used to determine the oxidation state of the surface metal atoms of LaCoO3 and Ru/LaCoO3 solids and to estimate their surface atom ratios in their reduced state (10 vol% H2 /N2 , 750 C, 2 h). Fig. 3a and b show XP spectra for the photoemission level of Co 2p measured for the reduced LaCoO3 and Ru/LaCoO3 solids, respectively. The XPS spectra presented in Fig. 3a and b for Co 2p core level appear to be practically the same for both solids investigated, having a multiple splitting at 778.5 and 794.1 eV which corresponds to 2p3/2 and 2p1/2 level, respectively. Shake-up peaks were also recorded around 786 and 802 eV, which are characteristic of Co2+ [20]. This species was formed after hydrogen reduction of the Ru/LaCoO3 solid (Section 2.2.2) indicating that a fraction of cobalt remains on its surface as Co2+ ions. In addition, the relative intensity of Co 2p shake-up peaks is larger in the case of LaCoO3 (Fig. 3a) than Ru/LaCoO3 solid (Fig. 3b). It is important to note that Co2+ ions are hardly reduced in the presence of water vapour, the latter generated either in the reduction process or during decomposition of lanthanum oxo-hydroxide (LaO(OH)) [21].

Co 2p

Ru/LaCoO3
770 780 790 800 810

Co 2p

LaCoO 3
770 780 790 800 810

Binding Energy (eV)


Fig. 3. X-ray photoelectron spectra of Co 2p obtained on the (a) pre-reduced LaCoO3 solid (10 vol% H2 /N2 gas mixture, 750 C, 2 h), and (b) pre-reduced Ru/LaCoO3 solid (10 vol% H2 /N2 gas mixture, 750 C, 2 h).

1. La2O3 2. La(OH)3 3. Co
I/Io (a.u.)
11

Table 2 presents values for the Co/La and (Ru + Co)/La surface atom ratio, and the adsorbed C/La surface ratio for the fresh reduced LaCoO3 and Ru/LaCoO3 solids. It is seen that LaCoO3 exhibits a higher metal/La ratio and a greater proportion of adsorbed C to surface La species compared to the Ru/LaCoO3 solid. These results will be further discussed in Section 3.1.5. 3.1.3. Metal dispersion measurements The amount of H2 desorbed (Section 2.2.4) from the surface of LaCoO3 and Ru/LaCoO3 solids was found to be 19.6 and 33.2 mol/g, respectively. This indicates that Ru/LaCoO3 solid exposed a higher amount of surface metallic phase (Ru, Co) per gram of solid than LaCoO3 after H2 reduction at 750 C. On the other hand, in both
Table 2 Surface atomic ratios calculated by XPS in LaCoO3 and Ru/LaCoO3 solids following H2 reduction at 750 C. Catalyst precursora Co/La or (Ru + Co)/La 1.10 0.85 Adsorbed C/La 0.59 0.41

1 12 3 1 1

2 1

Ru/LaCoO3

12 11 3

1 2

1 1

LaCoO3
60 70 80

10

20

30

40

50

2 ()
Fig. 2. XRD patterns of catalysts derived from LaCoO3 and Ru/LaCoO3 precursors after hydrogen reduction in a 10 vol% H2 /N2 gas mixture at 750 C for 2 h.

LaCoO3 Ru/LaCoO3

a Before XPS studies the solid catalyst was reduced in 10 vol% H2 N2 at 750 C for 2 h (Section 2.2.2).

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295

200

LaCoO3
CO Concentration (ppm)
150

(Table 3) for both solids. In the case of LaCoO3 the amount of desorbed CO was 0.9 mol/g compared to 14.6 mol/g of CO2 . This result is attributed to the formation of CO2 through the Boudouard reaction [22,23]: 2CO(g) + s CO2 (g) + C-s (1)

100

isothermal

Ru/LaCoO3
50

LaCoO3
0 100 300 500 700

The fact that reaction (1) takes place during CO-TPD has been reported for partially reduced LaCoO3 [23] as well as for -alumina [24] and silica-supported Ru solids [25]. Carbon dioxide can also be produced from the reaction between adsorbed carbon monoxide with surface hydroxyl groups of the metal oxide support located at the periphery of the metal-support interface, leading to the formation of CO2 and molecular hydrogen according to reaction (2) [26,27], and by surface reaction of adsorbed CO with surface labile oxygen (OL ) species (reactions (3) and (4)) [21,28]: COads + OHL CO2 (g) + 1/2H2 (g) (2) (3) (4)

Temperature (C)
600 500 400 300 200 100

b
LaCoO3

CO-s + OL

2e

CO2 -s

2e s /2e )

CO2 -s2e CO2 (g) + (

CO2 Concentration (ppm)

Ru/LaCoO3

isothermal
0 100 300 500 700

Temperature (C)
Fig. 4. (a) CO and (b) CO2 -TPD response curves obtained over LaCoO3 and Ru/LaCoO3 pre-reduced (10 vol% H2 /He, 750 C, 2 h) catalysts following adsorption of CO (2 vol% CO/He gas mixture, 30 min, 30 C).

cases metal dispersion values were very small (lower than 1%). Specically, metal dispersion was 0.4% and 0.8%, respectively for the LaCoO3 and Ru/LaCoO3 solids. These very low dispersion values are largely due to the presence of a large surface concentration of Co2+ and Run+ in both samples (no hydrogen chemisorption at 25 C takes place), in agreement with the XPS measurements in the case of Co2+ (Fig. 3) and the low BET values observed [10]; 3.3 m2 /g for LaCoO3 and 7.2 m2 /g for Ru/LaCoO3 . 3.1.4. CO chemisorption at 25 C followed by TPD Fig. 4a and b present CO and CO2 -TPD response curves, respectively, obtained over the LaCoO3 and Ru/LaCoO3 solids following chemisorption of CO at 25 C for 30 min (Section 2.2.5). Table 3 reports the quantities of CO and CO2 ( mol/g) estimated after integrating the respective TPD response curves and accounting also for the complete CO and CO2 desorption occurred isothermally at 700 C in He ow. The obtained results clearly indicate that a signicantly larger amount of CO2 was desorbed compared to CO
Table 3 Amounts ( mol/g) of CO and CO2 obtained over LaCoO3 and Ru/LaCoO3 solids following CO-TPD studies (Section 2.2.5). Catalyst precursora LaCoO3 Ru/LaCoO3 CO ( mol/g) 0.9 0.8 CO2 ( mol/g) 14.6 5.4

a Before CO chemisorption the solid catalyst was reduced in 10 vol% H2 /He at 750 C for 2 h (Section 2.2.5).

where s /2e is an oxygen vacant site. In the present work, very small H2 concentrations were detected (<10 ppm), thus reaction (2) is minor. In the case of LaCoO3 two sharp and well-resolved CO desorption peaks were observed (Fig. 4a) with peak maxima at 160 and 700 C (isothermal desorption). On the contrary, a very weak and broad desorption peak was detected for the Ru/LaCoO3 catalytic surface (Fig. 4a). The amount ( mol/g) of CO desorbed from the surface of both catalysts was approximately the same (Table 3). As reported by Gonzlez Tejuca et al. [21], the peak position of CO desorption (binding strength) is related to the oxidation state of cobalt and to the adsorption type of CO molecule (e.g., linearly or bridged CO). Following FTIR spectroscopic studies, Gonzlez Tejuca et al. [21] suggested that the rst low-temperature desorption peak obtained after interaction of CO or CO2 with the LaCoO3 surface could be assigned to monodentate carbonate, while the second peak to bridged carbonate. Similar results for the CO-TPD behaviour on LaCoO3 were reported by Rhee and Lee [28] during CO-TPD studies under vacuum conditions. The latter work reported also one low-temperature desorption peak (165 C) and a high-temperature one (360 C) with a tail out to 630 C. The authors suggested that the weak adsorption state of CO represents the bonding of CO with Co3+ via electron back-donation. The strong adsorption state of CO was assigned to a bridge-type CO bond with two lattice oxygens. According to what mentioned in the previous paragraph, the peak detected at 160 C for the pre-reduced LaCoO3 solid (Fig. 4a) could be attributed to linearly adsorbed CO on Co2+ , while the second peak at 700 C to bridge-type carbonate as evidenced by the CO2 desorption peak shown in Fig. 4b. However, it is also likely that some of adsorbed CO produced a small quantity of carbon via the Boudouard reaction (1). The latter may had reacted with lattice oxygen to form gaseous CO at high temperatures (ca. 700 C). The broad desorption trace of CO obtained for the catalyst derived after reduction of the Ru/LaCoO3 solid (Fig. 4a) clearly implies the inuence of the presence of Ru on the adsorption states of CO both on Ru and Co sites. Dulaurent et al. [29] reported that the modication of the Ru particles in the course of CO adsorption leads to new adsorbed states with heats of adsorption higher than that of the adsorbed species formed initially at 25 C. This important nding could explain the broadening of CO desorption trace in the case of Ru/LaCoO3 solid, where the interaction of Ru particles with support Co sites might have also inuenced the heat of adsorption of CO associated with the latter sites. The CO2 -TPD response curve obtained with the LaCoO3 solid (Fig. 4b) consists of an intense and broad peak centred at 600 C with a broad shoulder on its falling part. In the case of Ru/LaCoO3

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a largely different CO2 -TPD curve was obtained. More precisely, a very weak CO2 desorption peak centred at 35 C and a larger and broad one centred at 425 C with a shoulder on its rising part were detected (Fig. 4b). The amount of CO2 desorbed from the surface of LaCoO3 (14.6 mol/g) was found to be nearly three times larger than the amount of CO2 desorbed from the Ru/LaCoO3 surface (5.4 mol/g, Table 3). As stated in the previous paragraph, the formation of CO2 is the result of decomposition of bridge-type carbonate species formed upon CO chemisorption (reactions (3) and (4)). The latter is conrmed by the CO2 -TPDs to be presented in the following section. It appears from the CO-TPD results of Fig. 4 that the presence of Ru on the reduced LaCoO3 state retards signicantly the rate of carbon deposition via the Boudouard reaction and likely that of reaction of lattice oxygen of the oxidic phases present (e.g., La2 O3 ) with adsorbed CO. 3.1.5. CO2 chemisorption at 25 C followed by TPD CO2 chemisorption at 25 C followed by TPD (Section 2.2.6) was conducted following catalyst reduction at 300, 500 or 750 C for 2 h in order to create different concentration of oxygen vacancies in both solids, LaCoO3 and Ru/LaCoO3 . It is important to mention that for both solids and for all reduction temperatures studied no desorption of CO was observed. Fig. 5ac present CO2 -TPD response curves obtained following catalysts reduction at 300, 500 and 750 C, respectively. For both solids, all CO2 -TPD proles consist of two main desorption peaks; a small one in the low-temperature range of 25240 C, and a larger one in the high-temperature range of 200700 C with a shoulder at the falling part of it. In particular, Fig. 5a shows a weak CO2 desorption peak centred at 68 C and a broad one at 400 C in the case of Ru/LaCoO3 , while a sharp peak centred at 85 C and a broad one at 500 C with a shoulder on the rising and falling part of it were observed in the case of pre-reduced LaCoO3 catalyst. After increasing the hydrogen reduction temperature of Ru/LaCoO3 solid to 500 C (Fig. 5b), the CO2 desorption peaks were shifted to lower desorption temperatures compared to those detected when reduction of the solid occurred at 300 C (Fig. 5a). Therefore, the increase in reduction temperature from 300 to 500 C led to the decrease in the strength of surface basic sites, possibly due to the formation of surface and/or metal-support interface oxygen vacancies [30,31]. The opposite behaviour was observed for the LaCoO3 solid indicating desorption peaks with maxima at 92 and 512 C (Fig. 5b). After increasing the reduction temperature to 750 C (Fig. 5c), all CO2 desorption peaks related to LaCoO3 were shifted to higher temperatures when compared to those observed following H2 reduction at 500 C (Fig. 5b). The opposite behaviour was seen for the Ru/LaCoO3 which revealed peaks at 59 and 450 C close to the peaks observed after catalyst reduction at 300 C (Fig. 5a). It is concluded that the increase in H2 reduction temperature results in the increase of the strength of surface active basic sites in the case of LaCoO3 in agreement with previous studies [30,31]. On the other hand, in the case of Ru/LaCoO3 the strength of surface basic sites with increasing reduction temperature in the 300-750 C range passes through a minimum. The amount of desorbed CO2 ( mol/g) from the surface of each catalyst at the three different reduction temperatures applied is reported in Table 4. A slight increase (8%) of the surface basicity with increasing hydrogen reduction temperature in the 300750 C range was observed in the case of LaCoO3 catalyst. It is interesting to state that reduction of the Ru/LaCoO3 catalyst at 300 and 750 C resulted in the formation of a similar concentration of oxygen surface/interface basic sites. Moreover, the amount of desorbed CO2 from the surface of Ru/LaCoO3 solid was found to be ve to six times lower than that obtained for the LaCoO3 solid; a maximum amount of 4.8 mol CO2 /g was obtained for the Ru/LaCoO3 following hydrogen reduction at 300 or 750 C.

1800

Reduction 300C

CO2 Concentration (ppm)

1500 1200 900 600 300 0 100 300 500 700

LaCoO3
Ru/LaCoO3

isothermal

Temperature (C)
1800

Reduction 500C
CO2 Concentration (ppm)
1500 1200 900 600 300 0 100 300 500 700

LaCoO3
isothermal

Ru/LaCoO3

Temperature (C)
1800

Reduction 750C
CO2 Concentration (ppm)
1500 1200 900 600

LaCoO3

isothermal Ru/LaCoO3

300 0 100 300 500 700

Temperature (C)
Fig. 5. CO and CO2 -TPD response curves obtained over LaCoO3 and Ru/LaCoO3 prereduced catalysts (10 vol% H2 /He, T, 2 h) after CO2 adsorption (3 vol% CO2 /He gas mixture, 30 min, 30 C). Reduction T: (a) 300 C, (b) 500 C, and (c) 750 C.

Table 4 Amount ( mol/g) of CO2 adsorbed on LaCoO3 and Ru/LaCoO3 surfaces after hydrogen pre-treatment at 300, 500 and 750 C for 2 h, estimated after CO2 -TPD studies. Reduction temperature ( C) 300 500 750
a b

CO2 ( mol/g) 24.2a 4.8b 26.4a 3.8b 26.8a 4.8b

LaCoO3 . Ru/LaCoO3 .

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As stated earlier in Section 3.1.4, the rst CO2 desorption peak in the case of LaCoO3 is associated with monodentate carbonate adsorbed on Co2+ sites, whereas the second peak to bridged carbonate associated with surface Co2+ and La3+ cation sites. The shoulder observed in the high-T peak should also be associated with bridged carbonates known for their high thermal stability. According to the above mentioned, the higher concentration of CO2 accommodated on the surface of LaCoO3 compared to Ru/LaCoO3 indicates a greater surface concentration for Co2+ and/or La3+ derived from the reduced LaCoO3 compared to Ru/LaCoO3 solid. These results are in good agreement with other studies reported in the literature [32]. Moreover, the higher CO2 desorption temperatures observed over the pre-reduced LaCoO3 compared to Ru/LaCoO3 (Fig. 5) may have a role in the catalyst stability since adsorption of CO2 on lanthana leads to the formation of La2 O2 CO3 and formate species, which were reported to be involved in the gasication of carbon species formed during reaction [11,33]. The CO2 -TPD results obtained indicate that the LaCoO3 surface was less reduced compared to that of Ru/LaCoO3 as also revealed from the CO-TPD experiments (Fig. 4). The above observations are in agreement to those of less contribution of the shake-up peaks corresponding to Co2+ in the Ru/LaCoO3 than LaCoO3 solid as revealed in the XPS studies (Fig. 3). This is related to the higher reducibility of Ru/LaCoO3 solid structure compared to that of perovskite alone in agreement with results of previous work [10]. The higher surface proportion of Co2+ in the solid derived from the reduction of LaCoO3 is in agreement with the greater C/La atomic ratio found by XPS in the reduced samples, associated with the remaining carbonates formed on its surface after the reduction treatment (Table 2). All the above results strongly support the view that the increased amount of CO2 adsorbed, thus of the increased concentration of active basic sites formed on the surface of LaCoO3 compared to Ru/LaCoO3 following hydrogen pre-treatment is related to the increased concentration of surface Co2+ in the former solid due to the different degree of reduction achieved in the two solids. CO2 -TPD studies on clean LaCoO3 under vacuum conditions revealed only a single desorption peak (TM = 220 C) arising from the monodentate carbonate state [28]. In addition, a new adsorption state of CO2 was found to be formed during oxidation of CO on the LaCoO3 surface. These results could explain the differences in the position and shape of CO2 -TPD traces in the CO-TPD (Fig. 4) and CO2 -TPD (Fig. 5) experiments. 3.2. Catalytic performance of LaCoO3 and Ru/LaCoO3 towards oxidative steam reforming of propane The activity of pre-reduced in H2 at 750 C (Section 2.5) LaCoO3 and Ru/LaCoO3 catalysts towards the oxidative steam reforming (OSR) of propane was measured in terms of hydrogen yield (%) at 750 C (Fig. 6). Hydrogen yield is dened as the percentage of hydrogen composition formed experimentally with respect to the maximum theoretical hydrogen composition expected under the present feed gas composition used. It is seen (Fig. 6) that after 6 h on stream H2 -yields of 60% and 65% for LaCoO3 and Ru/LaCoO3 solids, respectively were obtained. The activity of both catalysts changes signicantly within the rst 4 h of reaction, and this is most likely due to the progressive increase in the extent of cobalt reduction. A slightly higher hydrogen production was found for the catalyst derived from LaCoO3 at the beginning of reaction, while a better performance was observed as reaction proceeded further for the catalyst derived from Ru/LaCoO3 . The latter should be partly related to the extent of reduction of Co2+ to Co0 in both catalyst compositions without considering the intrinsic activity of ruthenium phase. According to the present CO and CO2 -TPD studies, a greater proportion of unreduced cobalt was found in LaCoO3 than Ru/LaCoO3 catalytic system. It should be noted the slightly larger relative inten-

Ru/LaCoO3 LaCoO3
60

H 2 yield (%)

T=750C
40

Reaction Time (h)


Fig. 6. Hydrogen yield (%) versus reaction time obtained under oxidative steam reforming of propane performed at 750 C (GHSV = 20,000 h1 , H2 O/C = 3, O2 /C = 0.5 vol%) over the LaCoO3 and Ru/LaCoO3 solids pre-reduced in hydrogen (10 vol% H2 /N2 gas mixture, 750 C, 2 h).

sity of the satellite peaks of Co 2p shown in Fig. 3 which are related to the presence of Co2+ on the surface. Furthermore, the higher activity of catalyst derived from LaCoO3 should be inuenced by the larger amount of cobalt per gram of catalyst in the metallic state [10,34]. Even though the Ru + Co/La atomic ratio is lower than that of Co/La corresponding to the reduced system derived from LaCoO3 (Table 2), the catalyst containing Ru has a greater proportion of cobalt in the reduced state as indicated by the lower intensity of the satellite line associated with the principal peaks of the Co 2p doublet (Fig. 3b). The present results seem to indicate that the applied hydrogen reduction pre-treatment of the present LaCoO3 and Ru/LaCoO3 solids at 750 C does not ensure complete reduction of cobalt to Co0 . The presence of Co2+ contributes to re-adsorption of the CO and CO2 reaction products of OSR of propane reaction on the catalyst surface (Figs. 4 and 5), which is likely to have a suppressing effect (blockage of active sites) in the production of hydrogen during the OSR of propane reaction. It is well documented in the literature that water dissociation requires a pair site of Mx+ Oy on metal oxide surfaces, thus occupation of these sites by carbonates would reduce the rate of steam reforming reactions in general. 3.3. C3 H8 TPSR studies Propane TPSR experiments were conducted in order to investigate the interaction of the latter molecular species with the surface oxygen of the catalytic surfaces derived from LaCoO3 and Ru/LaCoO3 following different hydrogen or oxygen pre-treatments. Fig. 7 shows the evolution of mass spectrometer (MS) signals (m/z) recorded during propane TPSR over LaCoO3 , the latter pre-treated under three different conditions. More precisely, Fig. 7a and b present TPSR traces of m/z = 2 (H2 ), 16 (CH4 ), 28 (CO), 43 (C3 H8 ) and 44 (CO2 ) obtained over the pre-oxidized LaCoO3 at 600 and 400 C, respectively, while Fig. 7c shows the H2 -TPSR trace (m/z = 2) obtained over the pre-reduced LaCoO3 solid at 500 C. For the latter case it should be noted that all other m/z traces (16, 28, 43 and 44) obtained in the case of pre-oxidized solid were absent in the present case of pre-reduced solid, within the accuracy of the mass spectrometry analysis performed (see also Section 2.3). Fig. 8ac show similar C3 H8 -TPSR traces obtained over the Ru/LaCoO3 catalytic system. Reaction of propane over the catalytic surfaces derived from LaCoO3 and Ru/LaCoO3 following oxidation or reduction occurs with the surface oxygen ions (On ) present. Thus, the observed

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LaCoO3
1.5

T=700C oxidation 600C m/z=2 m/z=44 m/z=28 m/z=16 m/z=43


4 3

Ru/LaCoO3

T=700C m/z=2 oxidation 600C m/z=28

(a)

1.0

2 1 0

m/z=44 m/z=43 m/z=16

0.5

0.0 25 1.5 200 400 600

25 200 400 600

MS signal (x10 A)

MS signal (x10 10 A)

(b) m/z=2 m/z=44 m/z=16 m/z=43

oxidation 400C

4 3

10

b
m/z=44

m/z=2

oxidation 400C m/z=28

1.0

0.5

m/z=28

m/z=43
1 0 25 200 400 600

m/z=16

0.0 25 1.5 200 400 600

(c)

reduction 500C m/z=2

4 3

c
m/z=2

reduction 500C

1.0

2 0.5 1 0.0 25 200 400 600 0 25 200 400 600

Temperature (C)
Fig. 7. Temperature-programmed surface reaction (TPSR) of C3 H8 performed over LaCoO3 following oxidation at 600 C (a), 400 C (b), and hydrogen reduction at 750 C (c). Mass numbers (m/z): 2 (H2 ); 16 (CH4 ); 28 (CO); 43 (C3 H8 ); 44 (CO2 ).

Temperature (C)
Fig. 8. Temperature-programmed surface reaction (TPSR) of C3 H8 performed over Ru/LaCoO3 following oxidation at 600 C (a), 400 C (b), and hydrogen reduction at 750 C (c). Mass numbers (m/z): 2 (H2 ); 16 (CH4 ); 28 (CO); 43 (C3 H8 ); 44 (CO2 ).

intensities of MS signals associated with a given reaction product must depend on the catalysts BET surface area. It is evident from Figs. 7 and 8 that almost complete consumption of C3 H8 takes place from the beginning of TPSR (30 C). On the other hand, formation of H2 , CH4 , CO and CO2 gas products starts at T > 400 C. In particular, H2 formation starts between 400 and 450 C and increases with reaction temperature (400 700 C) and with time on stream at 700 C (isothermal reaction) in the case of pre-oxidized catalysts (Figs. 7a and b and 8a and b). On the other hand, a pseudo-steady state rate of H2 production is observed at lower temperatures over the pre-reduced than pre-oxidized solids but of similar magnitude (compare Fig. 7a and c). Furthermore, the general features of the TPSR trace for hydrogen formation are largely different in the case of pre-oxidized than pre-reduced solid. In particular, in the case of Ru/LaCoO3 the oxidative pre-treatment (Fig. 8a and b) led to a signicantly higher initial hydrogen formation rate at 700 C (isothermal conditions) compared to the reductive pre-treatment (Fig. 8c). However, as time on C3 H8 /He stream at 700 C increases, there is a larger drop in H2 formation rate for the pre-oxidized (600 C) than pre-reduced Ru/LaCoO3 solid (Figs. 8a and c). In the case of catalysts pre-treated in an oxidative atmosphere, a sudden increase in the H2 formation rate occurred after the catalyst was kept at 700 C under the C3 H8 /He feed stream for nearly 50 min (Figs. 7a and b and 8a and b). In this case, the formation of H2 is accompanied by a signicant increase of m/z = 28 (CO) signal but not of m/z = 44 (CO2 ) signal, the latter showing a decline with time on stream. These results indicate the formation of synthesis gas (CO/H2 ) via partial oxidation of propane by the aid of catalyst surface lattice oxygen. The formation of synthesis gas very likely partly reduces the perovskite structure of LaCoO3 to metallic cobalt formed on the surface of lanthana (Co/La2 O3 ), in agreement with

the XRD studies (Section 3.1.1). This reductive process favours further conversion of propane to CO/H2 , as evidenced by the evolution of the transient isothermal (T = 700 C) response curves of H2 and CO. This process of cobalt reduction that signicantly enhances syngas formation was found to be largely inuenced by the presence of Ru according to the results presented in Figs. 7a and 8a. 3.3.1. Mechanistic aspects of C3 H8 -TPSR As proposed in the literature [35] the propane-TPSR behaviour in perovskite-type materials (e.g., LaCoO3 ) for which an oxidative pre-treatment is performed could be explained by a two-stage process. In the rst stage, propane and lower hydrocarbons formed following propane cracking (e.g., CH4 , C2 H6 , C2 H4 ) react with surface lattice oxygen of the solid producing carbon monoxide, carbon dioxide and water according to reaction (5) in the case of propane. During this stage process, Co(III) is reduced to Co(II) and then to Co0 . In a following stage, non reacted propane could further react with metallic cobalt (Co0 ) formed producing hydrogen and propylene according to reaction (6), and other hydrocarbons, e.g., CH4 and C2 H4 according to reaction (7): C3 H8 + 9OL (lattice) CO + 2CO2 + 4H2 O + 9( (perovskite surface) C3 H8 H2 + C3 H6 (metal cobalt surface, Co0 ) C3 H8 CH4 + C2 H4 (metal cobalt surface, Co0 )
s /e

) (5) (6) (7)

Steam reforming of non reacted propane and of other hydrocarbons formed could also take place on the perovskite and cobalt surfaces, according to reaction (8) in the case of propane, where the

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water is provided via the combustion reaction (5). C3 H8 + 3H2 O 3CO + 7H2 (perovskite and metal cobalt surface, Co0 ) (8)

1.2 1.0

a
LaCoO3 T=600 C
o

CO2 Concentration (mol%)

The abrupt production of H2 tion of CO (Figs. 7a and 8a) can now be explained according to the above provided reaction scheme at the point where Co(III) reduction to Co0 was signicant, followed by selective reforming of Cx Hy into CO/H2 . It should be noted here that in the case of Ru/LaCoO3 , the Ru metal surface also participates in reactions described by Eqs. (6)(8). The MS signals recorded at m/z = 16 and 44 for both catalysts after oxidative pre-treatment (Figs. 7a and b and 8a and b) consist of two peaks with maxima between 400 and 700 C due to CH4 and CO2 formation. In the case of m/z = 44, since no propane (m/z = 43) is present at the exit of the reactor, this signal is due only to carbon dioxide. The rst peak of carbon dioxide should be related to the combustion of a fraction of produced methane and of other C2 hydrocarbons derived from propane cracking by the aid of surface lattice oxygen of perovskite, according to reaction (5), leading to partial reduction of cobalt (Co3+ to Co2+ ) as previously discussed. The second peak is most likely to be the result of combustion of propane with surface oxygen of the partially reduced perovskite, resulting in the reduction of Co2+ to metallic cobalt. Therefore, preoxidation of LaCoO3 and Ru/LaCoO3 seems to create new catalytic sites inuencing metallic cobalt formation during OSR of propane, thus to higher hydrogen production. The presence of Ru seems to play a positive role on this process. In the case of pre-reduction of LaCoO3 and Ru/LaCoO3 solids at 500 C before C3 H8 TPSR, neither CO, CO2 nor CH4 is formed under TPSR conditions or even under isothermal (T = 700 C) reaction of C3 H8 with the catalyst surface (Figs. 7c and 8c). This important result strongly suggests that all carbon-containing species formed upon propane decomposition are strongly held on the catalyst surface. The latter was probed by performing isothermal oxygen titration experiments to be described next. Based on the CO2 -TPDs described earlier (Fig. 5), it seems that the nature of these carbon-containing species is largely not adsorbed CO2 (e.g., carbonate species) but rather Cx Hy hydrocarbon fragments. It is to be noted that the differences observed in the various TPSR traces for LaCoO3 and Ru/LaCoO3 catalytic surfaces may not fully justify the difference (10%) in H2 -yield observed in Fig. 6 for the OSR of propane reaction performed over the same catalysts. However, this might be expected since in the present C3 H8 -TPSR experiments no H2 O and O2 were present in the feed. 3.4. Characterization of carbonaceous species formed after propane TPSR Isothermal oxygen titration (T = 600 C) studies following C3 H8 TPSR were contacted on the pre-oxidized solids at 600 C (Figs. 7a and 8a) in order to determine the amount of carbonaceous species accumulated on the surface of LaCoO3 and Ru/LaCoO3 due to cracking of propane itself and of other lower hydrocarbons (e.g., CH4 ) formed by cracking or de-hydrogenation of propane (e.g., C3 H6 and CH4 ; see reactions (6) and (7)). Fig. 9a and b show transient response curves of CO2 and CO, respectively, obtained under the ow of a 2 vol% O2 /He gas mixture at 600 C over LaCoO3. Similar transient response curves are shown in Fig. 10a and b for the Ru/LaCoO3 solid. Three distinct peaks of CO2 formation after 3, 33 and 43 min in O2 /He gas ow were observed in the case of LaCoO3 (Fig. 9a). On the other hand, in the case of CO formation (Fig. 9b) no dened peaks were obtained, where the CO production rate was practically constant for 30 min on stream. After that time, the rate started decreasing and became zero after 35 min on

at 700 C with concomitant produc-

0.8 0.6

0.4

0.2 0.0 0 10 20 30 40 50

He
5

2%O2 /He

Time (min)

CO Concentration (mol%)

LaCoO3
3

T=600 C

0 0 10 20 30

He

2%O2 /He

Time (min)

Fig. 9. CO2 (a) and CO (b) transient response curves obtained during isothermal (T = 600 C) oxygen titration of the carbon formed on the LaCoO3 (oxidative pretreatment at 600 C) after TPSR of propane.

stream. A different transient response curve of CO production was found for the Ru/LaCoO3 solid with prolonged period of time formation (50 min, Fig. 10b) and of decreasing rate. For the same catalyst, a large CO2 peak was observed with a maximum appearing after 40 min in O2 /He gas ow and with a broad shoulder in the lowreaction time side (Fig. 10a). It is interesting to note that the reaction rate of oxygen with carbonaceous species to form CO was slower in the case of Ru/LaCoO3 (Fig. 10b) compared to LaCoO3 (Fig. 9b). Furthermore, large differences are observed in the kinetic rate of oxidation of the carbonaceous species to form CO2 between LaCoO3 (Fig. 9a) and Ru/LaCoO3 (Fig. 10a) solids. The latter likely reects both the different chemical composition of carbonaceous species formed after C3 H8 -TPSR as evidenced by the three distinct CO2 peaks in the case of LaCoO3 (Fig. 9a), and the different kinetic rate constant (k) associated with the oxidation process in the two catalysts. Kinetic modelling of the isothermal transient oxidation experiments of Figs. 9 and 10 could lead to detailed characterization of the carbonaceous species formed as shown in previous studies [36,37] but this was out of the scope of the present work. The quantity ( mol/g) of carbonaceous deposits formed during the propane TPSR was obtained by integrating the respective transient CO and CO2 response curves (Figs. 9 and 10). This quantity could also be referred as percentage of the total carbon fed during the propane TPSR experiment and which was reactive in oxygen up to 600 C. The latter quantities of carbonaceous deposits were found to be 3.65 mmol/g or 38% of the total carbon fed for the

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7000 6000

a
Ru/LaCoO3

5000 4000 3000 2000 1000 0 0

T=600C

10

20

30

40

50

60

70

Time (min)

He
2.0

2%O2 /He

1.6

1.2

Ru/LaCoO3 T=600C
0.8

0.4

(a) CO and CO2 -TPD along with XPS studies conducted over prereduced (10% H2 /N2 gas mixture at 750 C for 2 h) LaCoO3 and Ru/LaCoO3 solids led to the conclusion that cobalt cannot be completely reduced to Co0 . (b) A greater fraction of unreduced Co2+ species was obtained for the solid derived from LaCoO3 after pre-reduction at 750 C for 2 h in 10% H2 /N2 gas mixture. This had a detrimental effect in the production of hydrogen in the oxidative steam reforming of propane since unreduced cobalt is not active towards the latter process. In addition, the presence of an increased surface concentration of Co2+ favours re-adsorption of the main reaction products, CO and CO2 which could eventually reduce catalyst activity by blocking active catalytic sites for water dissociation at least. (c) TPSR of propane indicated that surface lattice oxygen present in pre-oxidized LaCoO3 and Ru/LaCoO3 solids participate in the oxidation of propane which results in the formation of CO, CO2 , H2 and CH4 and carbonaceous deposits on the catalyst surface. It was found that the presence of Ru in the Ru/LaCoO3 solid composition largely reduces the rate of formation of carbonaceous deposits. Also, the kinetics of H2 formation was found to be largely inuenced by the catalyst pre-treatment performed (oxidation versus reduction) and largely promoted by the presence of Ru and of reduced cobalt phase. (d) Enhanced reactivity of propane over the Ru/LaCoO3 than LaCoO3 surface for either oxidative or reductive pre-treatments was observed during TPSR. It appears that the presence of Ru retards carbonaceous deposits and promotes syngas (CO/H2 ) formation. Acknowledgements

CO Concentration (mol%)

CO2 Concentration (ppm)

0.0 0 10 20 30 40 50

Time (min)

He

2%O2 /He

Fig. 10. CO2 (a) and CO (b) transient response curves obtained during isothermal (T = 600 C) oxygen titration of the carbon formed on the Ru/LaCoO3 (oxidative pre-treatment at 600 C) after TPSR of propane.

The Research Committee of the University of Cyprus is acknowledged for nancial support. Also, Dr. M. Consuelo lvarez-Galvn gratefully acknowledges nancial support from MCYT within the framework of the Ramon y Cajal research programme. We also thank Noelia Mota for performing the OSR of propane catalytic experiments. References
[1] S. Ahmed, M. Krumpelt, Int. J. Hydrogen Energy 26 (2001) 291. [2] D. Shekhawat, D.A. Berry, T.H. Gardner, J.J. Spivey, in: J.J. Spivey, K.M. Dooley (Eds.), Catalysis, The Royal Society of Chemistry, Cambridge, 2006, p. 184. [3] J.N. Armor, Appl. Catal. A: Gen. 176 (1999) 159. [4] P.K. Cheekatamarla, A.M. Lane, J. Power Sources 152 (2005) 256. [5] F. Brown, Int. J. Hydrogen Energy 26 (2001) 381. [6] A.F. Ghenciu, Curr. Opin. Solid State Mater. Sci. 6 (2002) 389. [7] D.J. Haynes, D.A. Berry, D. Shekhawat, J. Spivey, Catal. Today 136 (2008) 206. [8] T.H. Gardner, D. Shekhawat, D.A. Berry, M.W. Smith, M. Salazar, E.L. Kugler, Appl. Catal. A: Gen. 323 (2007) 1. [9] R.M. Navarro, M.A. Pena, J.L.G. Fierro, Chem. Rev. 107 (2007) 3952. [10] R.M. Navarro, M.C. Alvarez-Galvan, J.A. Villoria, I.D. Gonzlez-Jimnez, F. Rosa, J.L.G. Fierro, Appl. Catal. B: Environ. 73 (2007) 247. [11] A. Slagtern, Y. Schuurman, C. Leclercq, X. Verykios, C. Mirodatos, J. Catal. 172 (1997) 118. [12] A.N. Fatsikostas, D.I. Kondarides, X.E. Verykios, Catal. Today 75 (2002) 145. [13] D.-J. Liu, M. Krumpelt, Int. J. Appl. Ceram. Technol. 2 (2005) 301. [14] M.C. Alvarez-Galvan, R.M. Navarro, F. Rosa, Y. Briceno, F. Gordillo Alvarez, J.L.G. Fierro, Int. J. Hydrogen Energy 33 (2008) 652. [15] C. Palm, P. Cremer, R. Peters, D. Stolten, J. Power Sources 106 (2002) 231. [16] R.K. Kaila, A.O.I. Krause, Int. J. Hydrogen Energy 31 (2006) 1934. [17] A.L. Patterson, Phys. Rev. 56 (1939) 978. [18] C.D. Wagner, L.E. Davis, M.V. Zeller, J.A. Taylor, R.H. Raymond, L.H. Gale, Surf. Interface Anal. 3 (1981) 211. [19] C.N. Costa, T. Anastasiadou, A.M. Efstathiou, J. Catal. 194 (2000) 250. [20] J.F. Moulder, W.F. Stickle, P.E. Sobol, K.D. Bomben, in: J. Chastain (Ed.), Handbook of X-ray Photoelectron Spectroscopy, Perkin-Elmer Corporation, Eden Prairie, MN, 1992. [21] L. Gonzlez Tejuca, A.T. Bell, J.L.G. Fierro, M.A. Pena, Appl. Surf. Sci. 31 (1988) 301. [22] R.W. McCabe, L.D. Schmidt, Surf. Sci. 60 (1976) 85. [23] T. Arakawa, K. Takada, Y. Tsunemine, Mater. Res. Bull. 24 (1989) 395.

LaCoO3 solid, and 2.13 mmol/g or 17% for the Ru/LaCoO3 solid. The above results are in harmony with the lower carbon deposition observed in the Ru/LaCoO3 catalyst compared to LaCoO3 during the oxidative steam reforming of diesel [10]. Thus, it is evident from these studies that the role of Ru is to suppress signicantly the rate of formation of carbonaceous deposits during interaction of C3 H8 or higher hydrocarbons (e.g., those present in diesel) with surface lattice oxygen of Ru/LaCoO3 catalyst. It was reported [38] that Ru/TiO2 promotes the direct partial oxidation of CH4 to CO/H2 (no formation of CO2 and H2 O) as opposed to Ru/ -Al2 O3 which promotes the indirect route of partial oxidation (total oxidation of CH4 followed by steam and CO2 reforming of unconverted CH4 ). This result was interpreted based on DRIFTS studies which showed that the support inuenced in a detrimental manner the oxidation state of Ru; oxidized Ru sites promote the direct partial oxidation of CH4 to CO/H2 . In the present Ru/LaCoO3 (pre-oxidized catalyst) and Ru/La2 O3 Co/La2 O3 (pre-reduced Ru/LaCoO3 solid) systems, it is likely that the effect of support on the oxidation state of Ru inuences the oxidation rate of Cx Hy adsorbed species (formed upon propane chemisorption) towards H2 and COx (x = 1, 2).

4. Conclusions The following conclusions can be derived from the results of the present work:

M.C. lvarez-Galvn et al. / Applied Catalysis B: Environmental 102 (2011) 291301 [24] G.G. Low, A.T. Bell, J. Catal. 57 (1979) 397. [25] H. Yamasaki, Y. Kobori, S. Naito, T. Ohnishi, K. Tamaru, J. Chem. Soc. Faraday Trans. I 77 (1981) 2913. [26] T. Ioannides, X. Verykios, J. Catal. 140 (1993) 353. [27] A.M. Efstathiou, J. Mol. Catal. 69 (1991) 41. [28] C.K. Rhee, H.-I. Lee, Korean J. Chem. Eng. 11 (1994) 48. [29] O. Dulaurent, M. Nawdali, A. Bourane, D. Bianchi, Appl. Catal. A: Gen. 201 (2000) 271. [30] G. Zhang, H. Hattori, K. Tanabe, Appl. Catal. 36 (1988) 189. [31] K. Omata, A. Aoki, K. Fujimoto, Catal. Lett. 4 (1990) 241.

301

[32] L. Xiancai, W. Min, L. Zhihua, H. Fei, Appl. Catal A: Gen. 290 (2005) 81. [33] V.A. Tsipouriari, Z. Zhang, X.E. Verykios, J. Catal. 179 (1998) 283. [34] N. Mota, M.C. Alvarez-Galvan, J.A. Villoria, F. Rosa, J.L.G. Fierro, R.M. Navarro, Top. Catal. 52 (2009) 1995. [35] R. Jin, Y. Chen, W. Li, W. Cui, Y. Ji, C. Yu, Y. Jiang, Appl. Catal. A: Gen. 201 (2000) 71. [36] A.M. Efstathiou, D. Papageorgiou, X.E. Verykios, J. Catal. 141 (1993) 612. [37] V.A. Tsipouriari, A.M. Efstathiou, X.E. Verykios, J. Catal. 161 (1996) 31. [38] Y. Boucouvalas, Z.L. Zhang, A.M. Efstathiou, X.E. Verykios, Stud. Surf. Sci. Catal. 101 (1996) 443.

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