Carbon 45 (2007) 16451650 www.elsevier.

com/locate/carbon

The eect of phase separation in Fe/Mg/Al/O catalysts on the synthesis of DWCNTs from methane
Qiang Zhang, Weizhong Qian *, Qian Wen, Yi Liu, Dezheng Wang, Fei Wei
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China Received 26 January 2007; accepted 30 March 2007 Available online 11 April 2007

Abstract Double-walled carbon nanotubes (DWCNTs) were prepared by methane decomposition on Fe/Al/Mg/O catalysts with a xed iron loading of 1.5%. Increasing Al/Mg ratio in the catalyst resulted in the formation of a new MgAl2O4 phase, which was characterized by XRD. The size of the MgO crystallites in the support was decreased, due to the phase separation, from 35 nm to 20 nm in the Al/Mg ratio range of 0:14:1. At an Al/Mg ratio of 1:200, this eect prevented the sintering of iron on the MgO support and resulted in the synthesis of high-purity DWCNTs in high-yield. Very high-Al/Mg ratio induced the formation of the MgAl2O4 phase, which became another catalyst support material. This had a negative eect on the synthesis of DWCNTs due to its acidity and hardness. Simultaneously maintaining MgO as the dominant catalyst support and decreasing its particle size by the phase separation eect are important for good metal dispersion and, consequently, the yield and purity of DWCNTs. 2007 Elsevier Ltd. All rights reserved.

1. Introduction Chemical vapor deposition (CVD) is one of the most important methods to prepare double-walled carbon nanotubes (DWCNTs), which have extraordinary electrical conductivity, thermal conductivity, mechanical properties, and many potential applications. For CVD, many catalysts, e.g., Fe/MgO [1,2], Fe/Mo/MgO [37], Co/Mo/MgO porous catalysts [812], have been developed to decompose methane to make DWCNTs. These give yields of 10% 200%. The important factors for a good catalyst are the control of the loading of the active metal and maintaining a good metal dispersion on the catalyst support [13,5,9]. Generally, methods to highly disperse the metal crystallites on the support include tailoring the loading of the metal [3,6,12,19], protection using organic solvents during preparation [13,14], using promoters (e.g., Mo) [1517], and
Corresponding author. Fax: +86 10 62772051. E-mail addresses: qwz@otu.org, qianwz@mail.tsinghua.edu.cn (W. Qian). 0008-6223/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2007.03.045
*

using a stable and molecular-level uniform structure for the support [2,18,19]. However, the temperature for DWCNT synthesis is normally higher than 973 K where sintering of the metal crystallites and catalyst support are both serious due to the eect of Ostwald ripening. Typically, the sintering and loss of the surface area of the catalyst support are the main reason for the sintering of the metals. It can be imagined that with a larger sized catalyst support, the sintering of the metal on it will be much worse. Thus, if the catalyst support can be controlled to a relatively small size and the support particles separated from one another, e.g. during catalyst preparation or the DWCNT synthesis process [7,20], sintering of the metal crystallites can be eectively inhibited, which is favorable for the growth of DWCNTs with high-selectivity. Furthermore, another advantage of a small-sized catalyst support is that the growth of singlewalled carbon nanotubes (SWCNTs) on it is relatively facile [7,21], which favors the synthesis of SWCNTs with high-purity and yield. Thus, a method that controls the size of catalyst support will be very useful.

1646

Q. Zhang et al. / Carbon 45 (2007) 16451650

In the present work, we report a method to decrease the size of the catalyst support during the catalyst preparation, and its use in the synthesis of DWCNTs. The conceptual idea originates from the phase separation phenomenon in an alloy with the increase of the proportion of one component. In particular, an Fe/MgO catalyst was used as the model catalyst and MgO was the dominant support. On introducing Al species during catalyst preparation and tailoring of the Al/Mg ratio, the formation of a new MgAl2O4 phase in the MgO phase was observed. Due to the lattice mismatch between the MgO and MgAl2O4 phases, the size of the MgO support was gradually decreased by a phase separation eect. Using the catalyst with the optimum Al/Mg ratio, the yield and purity of DWCNTs can be dramatically increased. In addition, the complex relationship between the catalyst (with dierent Al/Mg ratios and acidity) and the dierent purities and yields of the as-grown carbon nanotubes is also reported. These ndings provide new concepts for the controlled synthesis of DWCNTs at a potentially low-cost.
2. Experimental
The Fe/Mg/Al/O catalyst was prepared by co-precipitation. A solution of Fe(NO3)3 9H2O, Mg(NO3)2 6H2O and Al(NO3)3 6H2O was precipitated from the base solution containing (NH4)2CO3 at 293353 K. After ltration, drying at 383 K for 20 h, and calcination at 673 K for 5 h, the catalysts were obtained as faintly yellow powders. Further details of the preparation of the catalyst were similar to that in Qian et al. [22]. To make CNTs, 100 mg catalyst was put into a quartz boat inserted in the center of a quartz tube reactor (id: 25 mm, length: 1200 mm). The reactor and the catalyst were heated to 873 K in Ar (ow rate of 600 ml/min), and H2 (ow rate of 50 ml/min) was then introduced into the reactor to reduce the catalyst for 30 min. After the catalyst reduction, the reactor was heated to 1273 K and a mixture of CH4 and H2 (100/50 ml/min, v/v) was introduced into the reactor. CH4 was decomposed on the catalyst to synthesize CNTs. This was continued for 60 min. Finally the reactor was cooled to ambient conditions in Ar. The catalyst was characterized by powder X-ray diraction (XRD, O8DISCOVER diractometer, nickel-ltered Cu Ka radiation, data recorded between 10 and 90). The crystallite size of the catalyst was calculated using the Scherrer equation. The morphology of the as-grown CNTs was characterized by high-resolution scanning electron microscopy (HRSEM, JSM 7401F, at 5.0 kV) and high-resolution transmission electron microscopy (HRTEM, JEM 2010, at 200.0 kV). Scattering Raman characterization of the CNTs was obtained using a Raman Microscope (Renishaw, RM2000, HeNe laser excitation line at 633.0 nm) at ambient conditions. TGA (TGA-2050) was used to characterize the purity and quality of the DWCNTs.

MgO MgAl2O4

Al /Mg

4:1 1:2

Intensity, a.u.

1:5

1:50

1:200

0:1 20 40 60 80

2-theta
Fig. 1. XRD patterns of Fe/Mg/Al/O catalysts.

tion method, the existence of the MgAl2O4 phase was clearly indicated in the XRD pattern when the Al ratio was higher than 20%. There was no obvious MgAl2O4 phase in the XRD pattern when the Al/Mg ratio was in the range of 1:501:200. Calculation of the size of the MgO crystallites indicated that the size was monotonously decreased with increasing Al/Mg ratio (Fig. 2). Specically, the size of the MgO crystallites could be decreased from 35 nm to 20 nm by changing the Al/Mg ratio to 4:1. Since
40

MgO crystalline /nm

35

30

3. Results and discussion Fig. 1 presented the XRD data for catalysts with dierent Al/Mg ratios before reduction. The catalyst without any Al species only had the peaks of the MgO crystal. The iron species at the low-loading (1.5%) was in an oxidized state and mainly formed an alloy with MgO, and dispersed uniformly in the support phase [23,24]. The size of the iron oxide crystallites was smaller than 3 nm, which was beyond the detection limit of XRD. However, on adding Al species into the Fe/MgO catalyst by the co-precipita-

25

20
-5 -4 -3 -2 -1 0

10

10

10

10

10

10

Al/Mg ratio
Fig. 2. Change of MgO crystalline size with the Al/Mg ratio in the catalyst.

Q. Zhang et al. / Carbon 45 (2007) 16451650

1647

the composite Al/Mg/O alloy did not change its size, we proposed here that MgAl2O4 phase, though in small amount, could be formed when the Al/Mg ratio was as small as 1:200. The results conrmed that a phase separation of the MgAl2O4 phase and MgO phase occurred in the entire range of Al/Mg ratio in the present work and conrmed our hypothesis that this eect is eective in decreasing the size of the catalyst support. It was also clear that when the Al/Mg ratio of the catalyst support was small, the MgO support was the dominant support, and when the Al/Mg ratio was higher than 1:4, the MgAl2O4 phase and MgO phase were both the dominant catalyst supports. The SEM images in Fig. 3 showed the morphology of the catalyst and as-grown CNTs on them. It was clear that the catalysts with low-Al/Mg ratios were sheet-like products (Fig. 3a and b). The catalysts with larger Al/Mg ratios in Fig. 3e and f were randomly distributed particles. These results also suggested that the size of the crystallites in the catalyst support was eectively decreased and these particles were kept separated from each other. Meanwhile, it was observed that CNTs in the form of relatively straight bundles were grown in large-amounts on the catalyst particles. In these images, no obvious multi-walled carbon nanotubes (MWCNTs) with large-diameters were observed, indicating the eective dispersion of the iron nanoparticles on the catalyst supports. HRTEM images (Fig. 4) showed that the products contained DWCNTs for all the catalysts used. The diameter of an individual tube was mainly 1.73.0 nm. The diameter of the DWCNT bundle was about 1030 nm. For the images in Fig. 4, we were unable to see any amorphous carbon that may adhere to the outer wall of the DWCNTs, which indicated the high-purity of the DWCNT products. It can also be deduced that if there existed amorphous carbon in the products, its formation will be at dierent active sites from those for the DWCNT growth. When the Al/Mg ratio was lower than 1:50, the outer diameters of most DWCNTs were near 2.0 nm. Increasing the Al ratio to higher than 1:5, the outer diameter of DWCNT was increased a little and the defects on these were also increased. As indicated by the XRD, the MgAl2O4 phase was formed and could be detected, which meant it had crystallites that reached a certain size and also was a catalyst carrier besides the MgO. Some active metal catalyst particles were present on the surface and had dierent sizes, which were sites for large-diameter CNTs or amorphous carbon due to the surface acidity [8]. Both the separation eect and the composition of the carrier aected the DWCNTs growth behavior. The Raman spectra in Fig. 5 provided a macroscopic analysis of the as-grown CNTs synthesized on the Fe/Mg/Al/O catalysts. There were RBM (radial breathing mode) peaks for all carbon products indicated that they all contained SWCNTs or DWCNTs. The very strong intensity of RBM peaks, for DWCNTs grown on the catalyst without Al and with the Al/Mg ratio of 1:200, indicated the strong excitation of DWCNTs of certain diameters by

Fig. 3. SEM images of carbon nanotubes on the Fe/Mg/Al/O catalysts. (Fe mole fraction was xed at 0.015, (a) Al/Mg = 0:1; (b) Al/Mg = 1:200; (c) Al/Mg = 1:50; (d) Al/Mg = 1:5; (e) Al/Mg = 1:2 and (f) Al/Mg = 4:1).

the laser, as compared with those of DWCNTs grown on other catalysts. Furthermore, we compared the intensity ratio of the D band to G band (ID/IG value) of the dierent samples (Fig. 6). It was clear that the ID/IG value was smallest for the DWCNTs grown on the catalyst with an Al/Mg ratio of 1:200, indicating the low-content of amorphous carbon and defects in this sample. However, when the Al/Mg ratio was increased, the ID/IG value also increased. Especially, when the Al/Mg ratio of the catalyst was 4:1, the ID/IG value of the as-grown carbon product was 0.8, a value that is close to that of MWCNTs [25].

1648

Q. Zhang et al. / Carbon 45 (2007) 16451650

Fig. 4. TEM images of carbon nanotubes synthesized on the Fe/Mg/Al/O catalysts (iron loading is 1.5 mol.%, (a) Al/Mg = 0:1; (b) Al/Mg = 1:200; (c) Al/Mg = 1:50; (d) Al/Mg = 1:5; (e) Al/Mg = 1:2 and (f) Al/Mg = 4:1).

0.3 0.8

Intensity (a.u.)

Yield of DWCNT

1:200 1:50 1:5 1:2 4:1

0.4 0.1 0.2

10
-6

500

1000

1500

2000

Raman shift (cm-1)

Fig. 5. Raman spectra of CNTs synthesized on the Fe/Mg/Al/O catalysts (iron loading is 1.5 mol %).

10

-4

10

-2

10

Al/Mg
Fig. 6. Relationship between ID/IG value and yield of carbon and the catalyst with dierent Al/Mg ratios.

In order to determine whether the carbon product was amorphous carbon or MWCNTs that was grown on the catalyst with high-Al/Mg ratios of 1:1 to 4:1, TGA analysis for these carbon products were performed and shown in Fig. 7. It was clear that the carbon products on the catalyst with large-Al/Mg ratios (1:14:1, especially for the later) were easily burnt in the low-temperature range (<400 C). This conrmed the high-content of amorphous carbon in the products on the catalyst with large-Al/Mg ratios (1:1 4:1). The results indicated that the MgAl2O4 phase was mainly responsible for the formation of amorphous carbon. In comparison, the carbon products synthesized by the catalysts with low-Al/Mg ratios had higher thermal oxidative stability and were burnt only at the high-temper-

ature range (>600 C). This indicated its high-content of DWCNTs with fewer defects in the product. These results were in agreement with the Raman spectra and SEM results. The formation of amorphous carbon on the catalysts with high-Al/Mg ratios can be mainly attributed to the acidity of the MgAl2O4 phase, as compared with that of the MgO phase. It is well known that alumina-containing supports (e.g., Al2O3, MgAl2O4 and many kinds of Al/Si zeolite) are acidic and are able to decompose a carbon source to produce amorphous carbon, as distinct from MgO and SiO2 supports [21]. Notably, this behavior is independent of the presence of metal crystallites on the

ID/IG

Al/Mg 0:1

0.2

0.6

Q. Zhang et al. / Carbon 45 (2007) 16451650

1649

1.00 0.95

4:1

0.90
Al/Mg

0.85 0.80 0.75

1:1

0:1 1:50 1:5 4:1 1:200

200

400

600

800

1000

Temperature /C
Fig. 7. TGA of CNTs over the Fe/Mg/Al/O catalysts (iron loading is 1.5 mol.%).

support. It is in agreement with our above observation that amorphous carbon does not adhere to the wall of the DWCNTs, but are from other active sites on the catalyst. Also, the diameter of the DWCNT and defect density of DWCNT also increased, as indicated by the HRTEM images. This is due to the dierences in catalyst behavior of the metal catalyst on the MgAl2O4 support. From this viewpoint, the MgAl2O4 support is not suitable for the preparation of DWCNTs, in contrast to the MgO support. The relationship between the DWCNT yield and the Al/ Mg ratio of the catalyst was calculated from the TGA results in Fig. 7. As shown in Fig. 6, the yield of DWCNTs was about 15% and 28% when grown from the catalyst without Al species and with an Al/Mg ratio of 1:200, respectively. The 70% increase in the DWCNT yield indicated the eectiveness of the phase separation eect decreasing the size of the MgO support from 35 nm to 30 nm. In this case, the MgO support was still the dominant support, and the newly formed MgAl2O4 phase presented in small amounts acts only to separate their crystallites from each other. In this case, the acidity of the MgAl2O4 phase did not seriously inuence the purity of the DWCNTs. However, with the further increase in the Al/Mg ratio of the catalyst, the situation was signicantly dierent. Although there was a monotonic decrease of the size of the MgO support with increasing Al/Mg ratio, the proportion of the MgAl2O4 phase also increased and it became another support for the iron particles. In this case, its acidity resulted in the transformation of the carbon source not into DWCNTs but into amorphous carbon, as discussed above. The diameter was increased, and the defects of DWCNTs were also increased with higher proportion of the MgAl2O4 phase. The purity of the DWCNTs was signicantly decreased. Even worse, MgAl2O4 is a stable spinel structure material with a Mohs hardness of 78, which is higher than that of MgO (about 46). When

MgAl2O4 was used as the support and iron crystallites dispersed on it or in its inner pores, DWCNTs did not grow facilely in its inner pores, which had been discussed in detail in Ref. [7], which caused more defects on DWCNTs as-grown products. Thus, the yield of DWCNTs was decreased (Fig. 6), a similar phenomenon to that can be seen in Refs. [7,24]. However, our analysis on the formation of defective DWCNTs from MgAl2O4 phase was qualitative. To this date, we are unable to distinguish the contribution of defective DWCNTs in Raman and TGA analyses quantitatively from those of amorphous carbon, though the content of amorphous carbon had the dominant eect on the low-purity of entire carbon products. Further investigation is needed. In this case, we proposed that the simultaneous maintenance of MgO as the dominant support material and decreasing its size were important for an increased yield and purity of DWCNTs. From this viewpoint, the addition of a small amount of Al species was sucient to break the texture of the MgO support and consequently to increase the purity and yield of the DWCNTs. Finally, it is noted that our catalyst is only a model catalyst used to show the phase separation eect. It showed that the eect can signicantly increase the yield of DWCNTs by 70%, though the actual carbon yield is relatively low. We believe that better results are possible if a catalyst with an intrinsically high-activity is used. Furthermore, our work also implies that the addition of other components in a small amount in the Fe/MgO catalyst can also be eective in decreasing the size of the MgO support. This provides a new alternative to increase the yield and purity of DWCNTs. The method is simple and reproducible and the catalyst can be mass produced for the controlled growth of DWCNTs at low-cost [26,27]. 4. Conclusions The introduction of Al species into an Fe/MgO catalyst by the co-precipitation method gave a decrease in the size of the MgO crystallites of the support from 35 nm to 20 nm with an increasing Al/Mg ratio, due to a phase separation eect between the newly formed MgAl2O4 phase and the MgO phase. The eect gave better dispersion of the metal crystallites on the MgO support. Consequently, the yield and purity of DWCNTs grown on the catalyst were increased by using a catalyst with an Al/Mg ratio of 1:200. However, further increase in the Al/MgO ratio of the catalyst led to the newly formed MgAl2O4 phase becoming another support material. Its acidity and hardness were both unfavorable for the formation of DWCNTs in high-yield and high-purity, although in its presence, the size of the MgO crystallites of the support was signicantly decreased. The results indicated that the keeping of MgO as the dominant support and decreasing the size of its crystallites simultaneously were important for the dispersion of the metal crystallites to favor the growth in DWCNTs with high-yield and high-purity.

Weight percentage

1650

Q. Zhang et al. / Carbon 45 (2007) 16451650 dened diameter distribution by chemical vapor deposition from alcohol. Carbon 2006;44(15):317782. Li QW, Yan H, Cheng Y, Zhang J, Liu ZF. A scalable CVD synthesis of high purity single walled carbon nanotubes with porous MgO as support material. J Mater Chem 2002;12(4):117983. Li YM, Kim W, Zhang YG, Rolandi M, Wang DW, Dai HJ. Growth of single walled carbon nanotubes from discrete catalytic nanoparticles of various sizes. J Phys Chem B 2001;105(46):1142431. Choi HC, Kundaria S, Wang DW, Javey A, Wang Q, Rolandi M, et al. Ecient formation of iron nanoparticle catalysts on silicon oxide by hydroxylamine for carbon nanotube synthesis and electronics. Nano Lett 2003;3(2):15761. Huang SM, Fu Q, An L, Liu J. Growth of aligned SWCNT arrays from water-soluble molecular clusters for nanotube device fabrication. Phys Chem Chem Phys 2004;6(6):10779. Kim W, Choi HC, Shim M, Li YM, Wang DW, Dai HJ. Synthesis of ultralong and high percentage of semiconducting single-walled carbon nanotubes. Nano Lett 2002;2(7):7038. Lu J, Kopley T, Moll N, Roitman D, Chamberlin D, Fu Q, et al. High-quality single-walled carbon nanotubes with small diameter, controlled density, and ordered locations using a polyferrocenylsilane block copolymer catalyst precursor. Chem Mater 2005;17(9): 22279. Wang X, Yue WB, He MS, Liu MH, Zhang J, Liu ZF. Bimetallic catalysts for the ecient growth of SWCNTs on surfaces. Chem Mater 2004;16(5):799805. Li QW, Yan H, Li XH, Zhang J, Liu ZF. High-density growth of single-walled carbon nanotubes on silicon by fabrication of nanosized catalyst thin lms. Chem Mater 2002;14(10):42626. Rolison DR. Catalytic nanoarchitectures The importance of nothing and the unimportance of periodicity. Science 2003; 299(5613):1698701. Bartholomew CH. Mechanisms of catalyst deactivation. Appl Catal A 2001;212(12):1760. Qian WZ, Liu T, Wei F, Wang ZW, Yu H. Carbon nanotubes containing iron and molybdenum particles as a catalyst for methane decomposition. Carbon 2003;41(4):8468. Liu JX, Ren Z, Duan LY, Xie YC. Eects of H2O on preparation of single-wall carbon nanotubes (SWCNT) by catalytic decomposition of CH4 in Ar. Acta Chim Sin 2004;62(8):77582 [in Chinese]. Zhou LP, Ohta K, Kuroda K, Lei N, Matsuishi K, Gao LZ, et al. Catalytic functions of Mo/Ni/MgO in the synthesis of thin carbon nanotubes. J Phys Chem B 2005;109(10):443947. Qian WZ, Liu T, Wei F, Yuan HY. Quantitative Raman characterization of the mixed samples of the single and multi-wall carbon nanotubes. Carbon 2003;41(9):18514. Wang Y, Wei F, Luo GH, Yu H, Gu GS. The large scale production of carbon nanotubes in a nano-agglomerate uidized bed reactor. Chem Phys Lett 2002;364(56):56872. Qian WZ, Wei F, Wang ZW, Liu T, Yu H, Luo GH, et al. Production of carbon nanotubes in a packed bed and a uidized bed. AICHE J 2003;49(3):61925.

Acknowledgements The work was supported by A Foundation for the Author of National Excellent Doctoral Dissertation of PR China (No. 200548), Natural Scientic Foundation of China (No. 20606020), China National program (No. 2006CB932702), Key Project of Chinese Ministry of Education (No. 106011) and National Center for Nanoscience and Technology of China. References
[1] Ago H, Nakamura K, Uehara N, Tsuji M. Roles of metal-support interaction in growth of single- and double-walled carbon nanotubes studied with diameter-controlled iron particles supported on MgO. J Phys Chem B 2004;108(49):1890815. [2] Ning GQ, Wei F, Wen Q, Luo GH, Wang Y, Jin Y. Improvement of Fe/MgO catalysts by calcination for the growth of single-and doublewalled carbon nanotubes. J Phys Chem B 2006;110(3):12015. [3] Lyu SC, Liu BC, Lee CJ, Kang HK, Yang CW, Park CY. Highquality double-walled carbon nanotubes produced by catalytic decomposition of benzene. Chem Mater 2003;15(20):39514. [4] Yu H, Zhang Q, Zhang QF, Wang QX, Ning GQ, Luo GH, et al. Eect of the reaction atmosphere on the diameter of single-walled carbon nanotubes produced by chemical vapor deposition. Carbon 2006;44(9):170612. [5] Li Y, Liu J, Wang YQ, Wang ZL. Preparation of monodispersed Fe Mo nanoparticles as the catalyst for CVD synthesis of carbon nanotubes. Chem Mater 2001;13(3):100814. [6] Lyu SC, Liu BC, Lee SH, Park CY, Kang HK, Yang CW, et al. Large-scale synthesis of high-quality double-walled carbon nanotubes by catalytic decomposition of n-hexane. J Phys Chem B 2004;108(7):2192214. [7] Wen Q, Qian WZ, Wei F, Liu Y, Ning GQ, Zhang Q. CO2-assisted SWCNT growth on porous catalysts. Chem Mater 2007;19(6): 122630. [8] Coquay P, Flahaut E, De Grave E, Peigney A, Vandenberghe RE, Laurent C. Fe/Co alloys for the catalytic chemical vapor deposition synthesis of single- and double-walled carbon nanotubes (CNTs). 2. The CNTFe/CoMgAl2O4 system. J Phys Chem B 2005;109(38): 1782530. [9] Flahaut E, Peigney A, Laurent C, Rousset A. Synthesis of single walled carbon nanotube-CoMgO composite powders and extraction of the nanotubes. J Mater Chem 2000;10(2):24952. [10] Ni L, Kuroda K, Zhou LP, Kizuka T, Ohta K, Matsuishi K, et al. Kinetic study of carbon nanotube synthesis over Mo/Co/MgO catalysts. Carbon 2006;44(11):226572. [11] Gru neis A, Ru mmeli MH, Kramberger C, Barreiro A, Pichler T, Pfeier R, et al. High quality double wall carbon nanotubes with a [12]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

[21] [22]

[23]

[24]

[25]

[26]

[27]