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NieSiO2 and NieFeeSiO2 catalysts for methane decomposition to prepare hydrogen and carbon laments
Wenhua Wang*, Heyi Wang, Yong Yang, Shubin Jiang
Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang, 621900 Sichuan, PR China

article info
Article history: Received 18 December 2011 Received in revised form 29 February 2012 Accepted 1 March 2012 Available online 29 March 2012 Keywords: Methane decomposition NieFeeSiO2 Carbon lament Hydrogen

abstract
Active and stable NieFeeSiO2 catalysts prepared by solegel method were employed for direct decomposition of undiluted methane to produce hydrogen and carbon laments at 823 K and 923 K. The results indicated that the lifetime of NieFeeSiO2 catalysts was much longer than NieSiO2 catalyst at a higher reaction temperature such as 923 K, however, a reverse trend was shown when methane decomposition took place at a lower reaction temperature such as 823 K. XRD studies suggested that iron atoms had entered into the Ni lattice and NieFe alloy was formed in NieFeeSiO2 catalysts. The structure of the carbon laments generated over NieSiO2 and NieFeeSiO2 was quite different. TEM studies showed that multi-walled carbon laments were formed over 75%Nie25%SiO2 catalyst, while bamboo-shaped carbon laments generated over 35%Nie40%Fee25%SiO2 catalysts at 923 K. Raman spectra of the generated carbons demonstrated that the graphitic order of the multi-walled carbon laments was lower than that of the bamboo-shaped carbon laments. Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

In recent years, the catalytic decomposition of methane to produce high-puried hydrogen and carbon laments has drawn lots of attention [1e4]. The hydrogen produced from methane decomposition can be directly used as the fuel for H2eO2 fuel cells for it doesnt contain any CO and CO2 [5e7]. The carbon laments are also widely used for its high mechanical strength, high resistance to strong acids and bases, high electric conductivity and high surface area [8]. The two products simultaneously obtained during methane decomposition make this reaction nancially attractive. Among the solid catalysts tested so far, Ni-based catalysts are believed to be the most effective for methane decomposition. Takenaka et al. [9] examined the catalytic performance of NieSiO2 catalysts with different Ni loadings and found that

the highest carbon yields (491 gC/gNi) were obtained over 40% Nie60%SiO2 at 773 K. Coprecipitated 90%Nie10%Al2O3 catalysts also exhibited considerable activity in methane decomposition at 773e823 K. The amounts of carbon laments formed over 90%Nie10%Al2O3 could reach as high as 111 gC/ gNi at 823 K[10]. However, the disadvantage of the Ni-based catalysts is that they are effective for methane decomposition in the temperature range of 673e873 K but are deactivated immediately at temperatures above 873 K [11]. While, the conversion of methane decomposition is not so high at reaction temperatures below 873 K for methane catalytic decomposition is an endothermic reaction and the conversion rises with the increase of the reaction temperature [12]. Further studies indicated that NieCu and PdeNi alloy catalysts showed a longer lifetime at a higher reaction temperature [13e16]. Fe-

* Corresponding author. Tel./fax: 86 816 2484200. E-mail address: Wangwenhua19860610@126.com (W. Wang). 0360-3199/$ e see front matter Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2012.03.003

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based catalysts can also decompose methane at a higher reaction temperature efciently as the activation temperature of the Fe-based catalysts is much higher than that of the Nibased catalysts [17]. The results of Ermakova et al. [18] suggested that there was no catalytic activity for Fe-based catalysts when reaction temperature was lower than 923 K. Although the overall catalytic performance of the Fe-based catalysts is not as good as that of the Ni-based catalysts, it can also be speculated that the introduction of the iron into Ni-based catalysts may extend the lifetime of the catalysts during methane decomposition at a higher reaction temperature. However, the catalytic performance of NieFe alloy catalysts hasnt been widely studied. In this work, NieFeeSiO2 catalysts with different contents of iron were prepared by solegel method. The inuences of the reaction temperature, the contents of iron and the CH4 ow rates on methane decomposition were studied. The morphological appearance, the compositions, the reducibility of NieFeeSiO2 catalysts and the carbon laments generated over NieSiO2 and NieFeeSiO2 catalysts during methane decomposition were investigated.

The morphological appearance of the catalysts and the deposited carbons were carried out in the FEI InspectF scanning electron microscope (SEM) operated at 20 kV. The detailed structure of the deposited carbons were observed using the JEOL JEM-100CX Transmission electronmicroscopy (TEM) and the Tecnai G2F20 Transmission electronmicroscopy (HRTEM), operated at 80 kV and 200 kV, respectively. Raman spectra were recorded on a DXR SmartRaman with 532 nm HeeNe ion laser as excitation source laser. The reducibility of the catalysts was measured in a quartz reactor with the temperature-programmed reduction (TPR) method. The quartz reactor with 30 mg of the catalyst was heated by an electrical furnace at a heating rate of 10 K/min in a 40 mL/min gas mixture containing 10%H2 and 90%Ar, at a maximum temperature of 973 K. Hydrogen consumption was measured by analyzing the efuent through a thermal conductivity detector.

3.

Results and discussion

2.
2.1.

Experimental
Catalysts preparation

3.1. Methane decomposition over NieSiO2 and NieFeeSiO2 catalysts

Fig. 1(a) depicts the kinetic curves of methane decomposition over NieSiO2 and NieFeeSiO2 catalysts at 923 K. Only hydrogen was obtained as a gaseous product over all the catalysts. The lifetime of the 75%Nie25%SiO2 catalyst without iron was very short at 923 K. After 70 minutes reaction, the methane conversion over 75%Nie25%SiO2 decreased to around 5%. The performance of this catalyst was a little worse than that of NieSiO2 which was prepared by Lazaro et al. [19]. Their catalyst prepared through the same method could catalyze methane decomposition at 973 K for 400 min. The reason for this difference might be that the amount of the catalysts they used during methane decomposition was 300 mg, while 50 mg of 75%Nie25%SiO2 was used in this reaction. The introduction of the iron improved the lifetime of NieSiO2 catalysts obviously, although a deactivation period also occurred for 65%Nie10%Fee25%SiO2 catalyst. When methane decomposition over 65%Nie10%Fee25%SiO2 catalyst proceeded to 200 min, the methane conversion decreased from 44% to 25%. As for methane decomposition over 35% Nie40%Fee25%SiO2 catalyst, the methane conversion maintained at 19% all the time which suggested that 35%Nie40% Fee25%SiO2 catalyst was very stable. Therefore, iron was a good modier for NieSiO2 catalysts to decompose methane and NieFeeSiO2 could catalyze methane decomposition at a higher reaction temperature such as 923 K. As the iron content increased in the catalyst, the catalytic activity of NieFeeSiO2 catalysts decreased while the stability of the NieFeeSiO2 catalysts was enhanced. Fig. 1(b) depicts the kinetic curves of methane decomposition over NieSiO2 and NieFeeSiO2 at 823 K. At a lower reaction temperature, 75%Nie25%SiO2 catalysts without iron also showed a longer lifetime and werent deactivated when methane decomposition proceeded to 400 min. The methane conversion over 65%Nie10%Fee25%SiO2 (18%) was a little

75%Nie25%SiO2, 65%Nie10%Fee25%SiO2 and 35%Nie40% Fee25%SiO2 catalysts (mass fraction) were prepared by a heterophase solegel method [19]. The method was based on mixing the active components such as NiO or mixture of NiO and Fe2O3 in this case, with alcosol containing silica in a certain amount. The suspends of the active components and alcosol were dried in owing air at room temperature and nally calcined at 923 K for 3 h. Alcosol was prepared by mixing 50 mL of TEOS, 40 mL of ethanol, 2 mL of water and 0.5 mL of 40%HCl. Silica content in the alcosol was 0.142 g/mL and could be diluted by ethanol. The mixture of NiO and Fe2O3 was originated from calcining the mixture of Ni(NO3)2 and Fe(NO3)3 at 723 K and the Ni(NO3)2 and Fe(NO3)3 mixtures were obtained by evaporating the solution of the mixed Ni(NO3)2 and Fe(NO3)3 at 373 K.

2.2.

Activity tests

Methane catalytic decomposition reactions were carried out in a xed-bed quartz reactor (10 mm i.d.) with the highpuried methane (99.99%) as feed stream under atmospheric pressure. Before the activity tests, all catalysts were subjected to a reduction pre-treatment using a ow rate of 20 mL/min of pure hydrogen for 1h at 923 K. The gaseous reaction products were monitored by gas chromatography (GC) combined with a 5A molecular column, using a thermal conductivity detector (TCD) for hydrogen and methane analysis.

2.3.

Catalysts characterization

XRD patterns were recorded on a Bruker D8Advance diffractometer with Cu Ka radiation at 40 kV and 40 mA.

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Fig. 1 e Kinetic curves of methane decomposition over NieSiO2 and NieFeeSiO2 catalysts ((a): 923 K, m(catalyst) [ 50 mg, v(CH4) [ 15 mL/min; (b):823 K, m(catalyst) [ 30 mg, v(CH4) [ 15 mL/min).

lower than that of 75%Nie25%SiO2 (22%). While, for the 35% Nie40%Fee25%SiO2 catalyst, the initial methane conversion was around 7% which was much lower than that of 75% Nie25%SiO2 and 65%Nie10%Fee25%SiO2 catalysts, and as the methane decomposition proceeded, the methane conversion decreased continuously. Thus, NieSiO2 and NieFeeSiO2 showed a reverse trend during methane decomposition at 823 K and 923 K. The NieFeeSiO2 catalysts were more suitable to catalyze methane decomposition at a higher reaction temperature. Fig. 2 shows the effect of the CH4 ow rate on methane decomposition over 65%Nie10%Fee25%SiO2 catalyst at 823 K. It can be observed that the catalytic activity of 65%Nie10% Fee25%SiO2 didnt change apparently during 400 min when the CH4 ow rate was 15 mL/min. The methane conversion over 65%Nie10%Fee25%SiO2 with 25 mL/min of CH4 ow rate

was close to that of 65%Nie10%Fee25%SiO2 with 15 mL/min of CH4 ow rate in the rst 110 min, however, the catalytic activity decreased gradually as the reaction continued and a slight deactivation took place. It can be speculated that the higher CH4 ow rates can decrease the methane conversion and reduce the lifespan of the 65%Nie10%Fee25%SiO2 catalyst during methane decomposition and this was in agreement with the results of Suelves et al. [20] and Domnguez et al. [21] pointed out that higher CH4 ow rates reduced the contact time between the CH4 molecules and the active centers present on the catalyst and then the conversion was impaired.

3.2. 3.2.1.

Characterization of the catalysts The morphological appearance of the catalysts

40 35 30

V(CH4)=15mL/min V(CH4)=25mL/min

Methane conversion(%)

25 20 15 10 5 0 0 50 100 150 200 250 300 350 400

The morphological appearance of the fresh and the reduced NieSiO2 and NieFeeSiO2 catalysts are displayed in Fig. 3. All samples appeared as large agglomerates of particles. It could be clearly observed that the size of the catalyst particles was highly inuenced by the iron content in the catalysts. The particles of lower content of iron catalyst such as the fresh and the reduced 65%Nie10%Fee25%SiO2 were smaller and more homogeneous than those of the fresh and the reduced 75%Nie25%SiO2. While the higher content of iron in the fresh and the reduced 35%Nie40%Fee25%SiO2 catalysts increased the particle size of the catalysts and the catalysts turned into big blocks.

3.2.2.

The compositions of the fresh and the reduced catalysts

t(min)
Fig. 2 e Effect of the CH4 ow rate on methane decomposition over 65%Nie10%Fee25%SiO2 (823 K, m(catalyst) [ 30 mg).

Fig. 4(a) shows the XRD spectra of the fresh NieSiO2 and NieFeeSiO2 catalysts. In the XRD spectra of the fresh 75% Nie25%SiO2 catalyst, the diffraction peaks due to NiO species were observed at 2q 32.21 , 43.25 , 62.82 , 75.34 and 79.32 indicating that Ni species in the fresh NieSiO2 catalyst were mainly present as NiO. No diffraction peaks due to SiO2 were observed which demonstrated that SiO2 in the catalysts existed in an amorphous state. Although iron was introduced, no Fe2O3 diffraction peaks were observed in the XRD patterns

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Fig. 3 e SEM images of NieFeeSiO2 catalysts with different iron contents (a: fresh 75%Nie25%SiO2; b: fresh 65%Nie10% Fee25%SiO2; c: fresh 35%Nie40%Fee25%SiO2; d: reduced 75%Nie25%SiO2; e: reduced 65%Nie10%Fee25%SiO2; f: reduced 35% Nie40%Fee25%SiO2).

of the fresh 65%Nie10%Fee25%SiO2 and 35%Nie40%Fee25% SiO2 catalysts. The iron in the fresh 65%Nie10%Fee25%SiO2 and 35%Nie40%Fee25%SiO2 catalysts mainly existed in the form of NiFe2O4 spinel. With the iron content increased from 10% to 40%, the intensity of NiFe2O4 peaks turned stronger while the intensity of NiO peaks dropped which suggested that more iron in the catalyst reacted with NiO to generate more NiFe2O4. Fig. 4(b) shows the XRD spectra of NieSiO2 and NieFeeSiO2 catalysts reduced by hydrogen. The diffraction peaks at 2q 44.46 , 51.81 and 76.36 in the XRD spectra of 75%Nie25% SiO2 revealed that Ni species in the reduced 75%Nie25%SiO2

catalyst existed mainly in the form of the metallic Ni. The diffraction peaks due to the iron were not detected even if the content of the iron was very high in the NieFeeSiO2 catalysts for the iron in the catalysts existed in the form of NieFe alloy. The NieFeeSiO2 catalysts reduced by hydrogen have two metal phases: the Ni metal phase and the NieFe alloy phase. The diffraction peaks due to NieFe alloy and Ni metal overlapped together which indicated that the NieFe alloy had identical structure with the Ni metal. Additionally, the NieFe alloy diffraction peak positions of NieFeeSiO2 catalyst shifted to a lower angle compared with Ni metal although this change was not very obvious and this suggested that the lattice

the fresh catalysts

the reduced catalysts

75%Ni-25%SiO

Intensity/cps
20

Intensity/cps

75%Ni-25%SiO

65%Ni-10%Fe-25%SiO

65%Ni-10%Fe-25%SiO
35%Ni-40%Fe-25%SiO
35%Ni-40%Fe-25%SiO

20

30

40

50

60

70

80

30

40

50

60

70

80

2/()

2/()

Fig. 4 e XRD spectra of the fresh and the reduced NieSiO2 and NieFeeSiO2 catalysts (- e NiO, C e NiFe2O4, : e Ni, A e NieFe alloy).

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Table 1 e X-ray diffraction data for NieSiO2 and NieFeeSiO2 catalysts. Fresh catalysts
75%Nie25%SiO2 65%Nie10%Fee25%SiO2 35%Nie40%Fee25%SiO2 Reduced catalysts 75%Nie25%SiO2 65%Nie10%Fee25%SiO2 35%Nie40%Fee25%SiO2

NiO lattice parameter (nm)

0.4177 0.4177 0.4177 Ni Lattice parameter (nm) 0.3524 0.3524 0.3524

NiFe2O4 lattice parameter (nm)

w 0.8377 0.8377 NieFe alloy lattice parameter (nm) w 0.3552 0.3598

NiO domain size (nm)

31.85 25.5 30.6 Ni domain size (nm) 25.87 13.2 25.2

NiFe2O4 domain size (nm)

w 10.25 13.1 NieFe alloy domain size (nm) w 10 23.87

parameters of the Ni crystal turned bigger when the iron atoms entered into the lattice of the Ni metal. Table 1 shows the XRD data of the fresh and reduced NiFe2O4 and NieFe alloy. As the iron content of the fresh NieFeeSiO2 catalysts increased from 0 to 10%, the domain size of NiO crystallite decreased from 31.85 nm to 25.5 nm, while as the iron content increased to 40%, the domain size of NiO particles increased to 30.6 nm. The domain size of NiFe2O4 increased from 10.25 nm to 13.1 nm with the rise of the iron content from 10% to 40%. Apparently, the NieFe alloy lattice parameter of the catalysts reduced by H2 was bigger than that of the Ni metal and with the increase of the iron content, the NieFe alloy lattice parameter turned even bigger. The Ni domain size of the NieFeeSiO2 catalysts reduced by hydrogen also showed a trend of rst decrease and then increase with the increase of the iron content which was similar with that of the NiO in the fresh catalysts.

3.2.3. The reducibility of the nickel and iron species in the fresh catalysts
The TPR proles of NieSiO2 and NieFeeSiO2 catalysts are shown in Fig. 5 to study the reducibility of the catalysts. A reduction peak at the temperature of 693 K and a shoulder peak at the temperature of 623 K were observed in the TPR

prole of 75%Nie25%SiO2 catalyst. Generally, for Ni-based catalysts the lower temperature peaks were attributed to the reduction of the bulk NiO particles without interaction with the support, while the higher temperature peaks were assigned to the reduction of NiO particles with chemical interaction with the support or other surface compounds [22]. Thus, the shoulder peak at 623 K of 75%Nie25%SiO2 was associated with the bulk NiO interacted with SiO2 slightly. While, the higher temperature peak at 693 K was attributed to NiO which strongly interacted with SiO2. A wider reduction peak began at 573 K and nished at 803 K with a maximum at 683 K for 65%Nie10%Fee25%SiO2 catalyst. A shoulder peak appeared at around 623 K which was similar with that of the 75%Nie25%SiO2 catalyst. Another shoulder peak appeared at 750 K which was attributed to the formation of NiFe2O4. The 35%Nie40%Fee25%SiO2 catalyst indicated a very different reduction behaviorda leading peak: the hydrogen consumption peak began from 593 K to 893 K and reached the maximum at around 823 K which suggested that the nickel and iron in the catalyst mainly existed in the form of NiFe2O4 species and this was in agreement with the XRD studies.

3.3. Characterization of the catalysts after methane decomposition

Fig. 6 shows the SEM images of the NieSiO2 and NieFeeSiO2 catalysts after methane decomposition at 823 K and 923 K, respectively. It could be clearly observed that the surface of catalyst was completely covered with interlaced carbon laments compared with the clean surfaces of the catalyst before the reaction (Fig. 3). The structure of the carbon laments was seriously inuenced by the reaction temperature and the introduced iron. The carbon laments generated over 75% Nie25%SiO2 catalysts at 823 K (Fig. 6(a)) were longer and thicker than those generated at 923 K (Fig. 6(b)). When the iron was introduced into the catalysts, the structure of the carbon laments also changed. At 823 K, the carbon laments generated over 35%Nie40%Fee25%SiO2 catalyst were thinner and shorter than those generated over 75%Nie25%SiO2 catalyst. While, at 923 K, the carbon laments generated over 35% Nie40%Fee25%SiO2 catalyst were much longer and more homogeneous than those generated over 75%Nie25%SiO2. Thus, it could be speculated that the carbon capacity of NieFeeSiO2 catalysts during methane decomposition at 923 K was higher than that of 75%Nie25%SiO2 and this might be the

35%Ni-40%Fe-25%SiO2

Hydrogen consumption

65%Ni-10%Fe-25%SiO2

75%Ni-25%SiO2

500

600

700

800

900

1000

T/K
Fig. 5 e Temperature programmed reduction proles of NieSiO2 and NieFeeSiO2 catalysts.

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Fig. 6 e SEM images of carbon laments generated over NieSiO2 and NieFeeSiO2 catalysts (a: 75%Nie25%SiO2, 823 K; b: 75% Nie25%SiO2, 923 K; c: 35%Nie40%Fee25%SiO2, 823 K; d: 35%Nie40%Fee25%SiO2, 923 K).

reason why NieFeeSiO2 catalyst showed a longer lifetime when methane decomposition took place at 923 K. Fig. 7(a) and (b) shows the TEM images of carbon laments generated by methane decomposition over 75%Nie25%SiO2 at 823 K and 923 K, respectively. In the TEM images of 75% Nie25%SiO2 after methane decomposition at 823 K (Fig. 7(a)), the carbon laments with diameters from 70 nm to 110 nm were observed. The pear-shaped Ni metal particles were present at the tip of the carbon laments. While in the TEM images of 75%Nie25%SiO2 catalyst after methane decomposition at 923 K (Fig. 7(b)), the diameter range of carbon laments was 50e90 nm and spherical Ni metal particles appeared at the tip of the carbon laments. The diameters of both types of carbon laments were similar to their diameters of the catalyst particles at the tips. Takenaka et al. [9] pointed out that Ni metal particles with smaller diameters were more effective for methane decomposition into hydrogen and carbon laments at a higher reaction temperature. This might be the reason why the carbon laments turned thinner as the reaction temperature become higher. Moreover, the different shapes of Ni metal particles at different reaction temperatures reected the different carbon diffusion mechanisms during methane decomposition. It was recognized by many researchers that methane decomposition and carbon growth over Ni-based catalysts included three stages: 1) activation and decomposition of methane on (1 0 0) and (1 1 0) metal surface planes, 2) carbon dissolution and

diffusion through the metal particles, 3) carbon segregation in the form of graphite-like phase on (1 1 1) nickel planes due to crystallographic matching of (1 1 1) nickel surface to (0 0 2) graphite planes [23]. Takenaka et al. [9] pointed out that the formation of the pear-shaped Ni metal particles was due to the diffusion of carbon atoms through the bulk of Ni metal particles and sh-bone carbon laments formed in this way, while the formation of the spherical Ni metal particles resulted from the diffusion of carbon atoms on the surface of Ni metal particles and multi-walled carbon laments formed in this way. Thus, it could be speculated that the carbon atoms generated during methane decomposition was preferential to diffuse through the surface of the Ni metal particles at a higher reaction temperature and the carbon structure changed with the change of the carbon diffusion mechanism. A clearer TEM images of multi-walled carbon laments generated over 75% Nie25%SiO2 at 923 K was shown in Fig. 8(a). Fig. 7(c) and (d) shows the TEM images of carbon laments generated by methane decomposition over 35%Nie40% Fee25%SiO2 catalyst at 823 K and 923 K, respectively. The structure of the carbon laments generated over 35%Nie40% Fee25%SiO2 catalyst at 823 K was similar with that of the carbon laments generated over 75%Nie25%SiO2 at 923 K, while the diameters of the carbon laments were a little smaller. Bamboo-shaped carbon laments formed during methane decomposition over 35%Nie40%Fee25%SiO2 catalyst at 923 K$ The wall of the bamboo-shaped carbon laments

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Fig. 7 e TEM images of carbon laments generated over NieSiO2 and NieFeeSiO2 (a: 75%Nie25%SiO2, 823 K; b: 75%Nie25% SiO2, 923 K; c: 35%Nie40%Fee25%SiO2, 823 K; d: 35%Nie40%Fee25%SiO2, 923 K).

were uneven and the hollows of these carbon laments were divided into many cells which was different from those generated over 75%Nie25%SiO2 catalyst. The NieFe alloy particles which were active for methane decomposition were not only present at the tip of the carbon laments after methane decomposition, but also existed in the hollow cells of the bamboo-shaped structure. A clearer bamboo-shaped

carbon laments was also shown in Fig. 8(b). Apparently, the addition of the iron changed the carbon deposition mechanism of NieSiO2. The results of Takenaka et al. [17] indicated that the products of methane decomposition over FeeSiO2 catalysts were also bamboo-shaped carbon laments. Thus, the carbon deposition mechanism of NieFeeSiO2 was similar with that of FeeSiO2 catalyst.

Fig. 8 e HRTEM images of carbon laments generated over NieSiO2 and NieFeeSiO2 at 923 K (a: 75%Nie25%SiO2; b: 35% Nie40%Fee25%SiO2).

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Ermakova et al. [24] pointed out that the carbon growth over FeeSiO2 catalysts did not need a specic set of edges, as it did in the case of nickel. The iron particles might be liquid during methane decomposition. When methane decomposition over the FeeSiO2 catalyst took place at 873e1073 K, iron carbide generated rapidly. However, the iron carbide was not stable and decomposition of the unstable carbide made the iron particles supersaturation with carbon and the graphitic nucleus appeared. With the formation and decomposition of the iron carbide continuously, other carbon generated assembled around the former nucleus for the nucleation must overcome a high activation barrier. Along with the accumulation of the carbon a part of the iron particle covered with graphite gradually extended and become narrower and narrower. At the same time, the orientation of the graphite layers also transformed from parallel to the iron particle surface to perpendicular to the iron particle surface gradually and a bamboo node of the carbon laments nally formed in this way. Fig. 9 shows the raman spectra of the 75%Nie25%SiO2 and 35%Nie40%Fee25%SiO2 catalysts after methane decomposition at 823 K and 923 K. For all the carbon deposited over different catalysts at different reaction temperatures, two bands were clearly observed at 1350 cm1 (D band) and 1580 cm1 (G band), respectively. The G band at 1580 cm1 was attributed to the in plane carbonecarbon-stretching vibration of graphitic layers and the D band at 1580 cm1 was ascribed to the structural imperfection of the graphite. A shoulder peak (D0 band) in G band was also found at 1615 cm1 which was also assigned to be the imperfect graphite or disordered carbons [25,26]. Table 2 shows the ratio of the area of D band to that of the G band (ID/IG) for different carbon laments generated over NieSiO2 and NieFeeSiO2 catalysts The ID/IG value could be regarded as a symbol for the crystalline order of graphite. The reaction temperature and the introduced iron strongly

Table 2 e Changes in ratio of area of the D band to that of the G band (ID/IG) in Raman spectra of carbon laments generated over 75%Nie25%SiO2 and 35%Nie40%Fee25% SiO2. Temperature (K)
823 923

ID/IG (75%Nie25% SiO2)

1.25 0.935

ID/IG (35%Nie40% Fee25%SiO2)

1.13 0.745

affected the crystalline order of the generated graphite. For the carbon laments generated over 75%Nie25%SiO2, the ID/IG value decreased as the reaction temperature increased, indicating that the graphitic order of the carbon laments become higher with the rise in the reaction temperature and this was in agreement with Echegoyens results [9]. Thus, the graphitic order of the multi-walled carbon laments generated at a higher reaction temperature was higher than that of the sh-bone type laments. When the iron was introduced into NieSiO2 catalysts, the graphitic order of the carbon laments generated at both 823 K and 923 K become higher. It could also be speculated that the bamboo-shaped carbon laments should be more perfect than the multi-walled carbon laments.

4.

Conclusions

D band

G band

D' band

35%Ni-40%Fe-25%SiO2,823K

1) The introduction of the iron into NieSiO2 catalysts obviously extended the lifetime of the catalysts at 923 K during methane decomposition. However, a reverse trend was shown when methane decomposition took place at a lower reaction temperature such as 823 K. 2) XRD studies of NieFeeSiO2 catalysts reduced by hydrogen indicated that NieFe alloy was formed when iron was introduced into NieSiO2 catalyst. 3) The structure of the carbon laments formed over NieSiO2 and NieFeeSiO2 catalysts was different. At 923 K, multiwalled carbon laments were generated over 75%Nie25% SiO2 catalyst, while bamboo-shaped carbon laments were generated over 35%Nie40%Fee25%SiO2 catalysts. The graphitic order of bamboo-shaped carbon laments was higher than that of the multi-walled carbon laments.

intensity(a.u.)

75%Ni-25%SiO ,823K
2

Acknowledgements
35%Ni-40%Fe-25%SiO ,923K
2

This work was nancially supported by the National Magnetic Connement Fusion Science Program of China (2011GB111005) and National Natural Science Foundation of China (11075134).

75%Ni-25%SiO ,923K
2

references

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1400

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1600
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Raman shift(cm )
Fig. 9 e Raman spectra of carbon laments obtained over NieSiO2 and NieFeeSiO2 catalysts.

[1] Otsuka K, Ogihara H, Takenaka S. Decomposition of methane over Ni catalysts supported on carbon bers formed from different hydrocarbons. Carbon 2003;41(2):223e33. [2] Takenaka S, Ogihara H, Otsuka K. Structural change of Ni species in Ni/SiO2 catalyst during decomposition of methane. J Catal 2003;208(1):54e63.

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