Materials Research Bulletin 42 (2007) 14851491 www.elsevier.

com/locate/matresbu

Synthesis of polyoxometalates-functionalized carbon nanotubes composites and relevant electrochemical properties study
Yanli Song, Enbo Wang *, Zhenhui Kang, Yang Lan, Chungui Tian
Institute of Polyoxometalate Chemistry, Department of Chemistry, Northeast Normal University, Changchun Jilin 130024, PR China Received 24 May 2006; received in revised form 24 October 2006; accepted 1 November 2006 Available online 18 December 2006

Abstract Carbon nanotubes (CNTs)-based polyoxometalates (POMs)-functionalized nanocomposites were synthesized by simply functionalizing CNTs with Keggin and Dawson-type POMs. The positively charged polyelectrolyte poly (diallyldimethylammonium chloride) (PDDA) was introduced to assemble negatively charged POMs and CNTs. The composition, structure and morphology were investigated by UVvisible (UVvis), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). Cyclic voltammetry (CV) was employed to investigate the electrochemical properties of the resulting nanocomposites. The cyclic voltammograms indicate that the electrochemical properties of POMs are fully maintained. Functionalizing CNTs with POMs not only retains the unique properties of nanotubes, but also endows CNTs with the reversible redox activity of POMs. # 2006 Elsevier Ltd. All rights reserved.
Keywords: A. Composites; A. Nanostructures; B. Electrochemical properties

1. Introduction During the past decades nanometer-scale materials have attracted considerable interest due to their fundamental signicance for physical properties and potential applications owing to their unique particle sizes and surface effects [1]. Up to now, a variety of techniques have been applied to fabricate nanostructures of a broad class of materials, ranging from semiconductors, metal oxides to metal nanoparticles with different morphologies [2]. However, some of the proposed applications of these nanomaterials remain a far-off dream; others are closed to technical realization. Recent developments of reliable strategies for functionalizing and processing the nanomaterials provide an additional impetus towards extending the scope of their applications [3]. More and more efforts have been paid to functionalize nanomaterials since the functional properties of the obtained nanoscaled composites are greatly improved compared with the original materials [4]. Since the discovery of carbon nanotubes (CNTs) [5], they have triggered intensive research for their unique properties including high surface area, specic electrical conductivity, exceptional physicochemical stability and signicant mechanical strength. In fact, as the best and most available one-dimensional (1D) nanomaterials, carbon nanotubes show wide applications in material science, sensor technology, catalysis and biomedical elds [6]. However, electrochemical inertness and low chemical reactivity of raw nanotubes lead to the basal limitations of their
* Corresponding author. Tel.: +86 431 5098787; fax: +86 431 5098787. E-mail address: wangenbo@public.cc.jl.cn (E. Wang). 0025-5408/$ see front matter # 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.materresbull.2006.11.001

1486

Y. Song et al. / Materials Research Bulletin 42 (2007) 14851491

applications [7]. Enhancing the activity and extending the applications of carbon nanotubes show strong dependence on the development of methods for functionalizing and processing these nanotubes. Recently, several methods have been reported for the attachment of nanoparticles, biomacromolecule and other functional materials with various natures onto CNTs [8]. The obtained functionalized nanocomposites preserve the unique properties of the nanotubes, simultaneously endowing the materials with novel functions that cannot otherwise be acquired by raw nanotubes [3]. Polyoxometalates (POMs), a class of molecularly dened inorganic metal oxide clusters, have won particular attention for their various applications in many elds of science, such as medicine, biology, catalysis, and materials owing to their chemical, structural, and electronic versatility [9]. Accordingly, the development of POMs-containing functional nanomaterials and nanodevices is steadily increasing [10], and the functional properties have also been investigated, which provide a spark to the combination of nanoscience and polyoxometalates chemistry. On the basis of the excellent redox properties and the high protonic conductivity of polyoxometalates, both Kegginand Dawson-type heteropolyanions have been extensively applied as highly selective and long-time stable redox catalysts [11]. Therefore, functionalizing CNTs with POMs will make CNTs more attractive in catalysis and electrochemistry elds by comparison with pristine nanotubes. The reported POMs-functionalized nanocomposites exhibit voltammetric response in the potential window commonly used, which indicates that the electrochemical properties of POMs may be fully maintained when they are introduced to functionalize CNTs [12]. Hence, CNTs-based nanocomposites bearing POMs with redox activity are of potential importance to electrocatalysis and charge storage in redox capacitors. In the present work, three types of POMs were chosen to prepare CNTs-based POMs-functionalized nanocomposites on the basis of electrostatic interactions. The positively charged polyelectrolyte PDDAwas used to assemble negatively charged POMs and CNTs, and the obtained nanocomposites were expressed with CNTs-PDDA/POMs. 2. Experimental 2.1. Chemicals CNTs with diameters of 1520 nm were purchased from Tsinghua-Nane Nano-power Commercialization Engineering Center. Poly (diallyldimethylammonium chloride) (PDDA, 20% in water, MW  100,0002,000,000) was purchased from Aldrich and used as received. Polyoxometalates (POMs) with the composition H3PMo12O40 14H2O (abbreviated PMo12), K4SiW12O4014H2O (abbreviated SiW12), (NH4)6P2Mo18O6214H2O (abbreviated P2Mo18) were synthesized according to the literature procedure [13]. Hydrochloric acid (HCl, 37%), sulfuric acid (H2SO4, 98%), nitric acid (HNO3, 70%), and sodium bromide (NaBr, AR), were all purchased from commercial market and used without further purication. 2.2. Instruments An AA10200A ultrasonic cleaner was used to oxidative cutting CNTs and coating CNTs with polyelectrolyte. UV vis absorption spectra were recorded on a 756 PC UVvis spectrophotometer. FTIR patterns were measured in the range 4004000 cm1 on an Alpha Centauri FTIR spectrophotometer. TEM images were obtained using a JEM-2010 transmission electron microscope at an acceleration voltage of 200 kV. A CHI 660-electrochemical workstation connected to a digital-586 personal computer was used for the control of the electrochemical measurements and for data collection. A conventional three-electrode cell, consisting a carbon paste electrode (CPE) as the working electrode, a saturated calomel electrode (SCE) served as reference electrode and a platinum foil was applied as the counter electrode. All potentials were measured and reported versus the SCE. 2.3. Fabrication of CNs-PDDA/POMs nanocomposites The received CNTs were sonicated with 37% hydrochloric acid (HCl) for 2 h to remove the catalysts (support and metal particles). The precipitate was kept overnight and then diluted with deionized water. The obtained mixture was chemically oxidized by ultrasonication in a mixture of sulfuric acid and nitric acid (3:1) for 8 h, and then washed with deionized water and separated by centrifuging/washing till the pH  7. After being dried in vacuum at 60 8C, the oxidative CNTs were dispersed in deionized water. In this work, PDDA was dissolved in deionized water at a concentration of 0.1 mg/mL, and then the CNTs bearing carboxylic groups were coated with PDDA through

Y. Song et al. / Materials Research Bulletin 42 (2007) 14851491

1487

Scheme 1. Schematic illustration of the procedures for the fabrication of PDDA-CNTs/POMs nanocomposites. (Step a) Ultrasonic oxidation of CNTs in a mixture of sulfuric acid and nitric acid (3:1). (Step b) Deposition of PDDA on negatively charged CNTs with formation of CNTs-PDDA nanohybrid materials. (Step c) Adsorption of POMs to functionalize PDDA-wrapping CNTs.

dispersing CNTs in PDDA solutions for 3 h with sonication. The obtained PDDA-wrapped CNTs formed stable, uniform aqueous solution and did not precipitate for at least 12 h [14]. As demonstrated in the literature, POMs can combine with PDDA via electrostatic action forming small domains [15]. Electrolyte NaBr was added to separate excess polyelectrolyte from PDDA-CNTs, the mixture was centrifugated three times and the supernatant solution was decanted. POMs (SiW12, PMo12, P2Mo18) was subsequently deposited by redispersing PDDA coated CNTs nanohybrid materials in 0.1 M POMs aqueous solution with sonication for 1 h. The last procedure was carried out by three repeated centrifugation/wash cycles. Then, the black precipitate was dried in vacuum. 3. Results and discussion Scheme 1 illustrates the preparation procedure of the nanocomposites. The oxidatively treated CNTs were negatively charged owing to the anionic carboxylic acid groups generated at both the defect sites along the side walls and the open ends of the tubes [16], and the carbon nanotubes were shortened at the same time. The driving force for the formation of CNTs-PDDA/SiW12 is electrostatic attraction between oppositely charged species. The reaction mechanism is similar to the mechanism of LbL technique rst introduced by Decher [17] and can be described as follows: negatively charged CNTs interact with cationic polyelectrolyte PDDA and form carboxylates, then anionic POMs absorb on CNTs by combining with PDDA. Fig. 1(a) displays typical TEM images of raw CNTs, while Fig. 1(b) and (c) show lower and higher magnication images of CNTs-PDDA/SiW12 nanocomposites. As shown in Fig. 1, the surface of raw CNTs was smooth but when POMs deposited on CNTs small domains formed, which is owing to the aggregation of POMs in the presence of PDDA [15]. The as-prepared products were characterized by UVvis spectroscopy. Fig. 2 shows the UVvis spectra of the raw CNTs (a), CNTs-PDDA (b) and CNTs-PDDA/POMs (c), respectively. The broad peak around 240 nm can be assigned

Fig. 1. TEM images of CNTs (a) and CNTs-PDDA/SiW12 nanocomposites (b) lower and (c) higher magnication.

1488

Y. Song et al. / Materials Research Bulletin 42 (2007) 14851491

Fig. 2. UVvis spectra of raw CNTs (a); CNTs-PDDA (b); CNTs-PDDA/SiW12 (c-1), CNTs-PDDA/PMo12 (c-2), and CNTs-PDDA/P2Mo18 (c-3).

Y. Song et al. / Materials Research Bulletin 42 (2007) 14851491

1489

to the absorption of CNTs suspended in ethanol [18]. However, the absorption wave shifted to 267 nm when CNTPDDA formed, which is consistent with literature [19]. As shown in Fig. 2(c)-1, the remarkable peaks at 200, 260 nm attributed to the oxygen ! tungsten charge transfer (CT) transition of SiW12. Furthermore, in Fig. 2(c)-2, the Od ! Mo and Ob (Oc) ! Mo charge transfer (CT) transition of PMo12 are observed at 215 and 325 nm, while two peaks at 212 and 320 nm in Fig. 2(c)-3 are the characteristic absorption of P2Mo18. The combined results demonstrate that the expectant products have been synthesized. Fourier transform infrared spectroscopy is an effective characterization method to reveal the composition of the products. The IR spectrum of CNTs was shown in Fig. 3(a)-1, the band at 1725 cm1 is attributed to the C O stretch mode of carboxylic acid groups, which demonstrates the formation of carboxyl on CNTs. In Fig. 3(a)-2, six peaks were observed in the IR spectrum of CNTs-PDDA, the ns(OH), nas(CH2), ns(CH2), d(CH2) and n(CN) appeared at 3435, 2922, 2855, 1458 and 138 4 cm1, respectively. Furthermore, the peak at 1636 cm1 can be assigned to carboxylates according to the nas(RCOOR0 ) at 16501545 cm1 [20]. The results above combined further veried the formation of CNTs-PDDA nanohybrid materials. In Fig. 3(b)-1, the four characteristic peaks at 974, 921, 884 and 790 cm1 are attributed to n(W Od), n(SiOa), n(WObW), n(WOcW), respectively. As shown in Fig. 3(b)-2, the bands at 1061, 958, 878, 792 cm1are the characteristic peaks of PMo12, while six characteristic bands of P2Mo18 were observed at 1077, 1003, 940, 905, 834, 777 cm1 in Fig. 3(b)-3. All of the results attest the adsorption of POMs clusters on the PDDA-wrapped CNTs and the basic structure of POMs are still preserved in the nanocomposites [21]. The electrochemical behavior of CNTs-PDDA/POMs nanocomposites was investigated by fabricating carbon paste electrode (CPE). The CPE was fabricated according to the literature [22]. Fig. 4 shows the cyclic voltammograms of

Fig. 3. IR spectra of the CNTs (a-1) and CNTs-PDDA (a-2); CNTs-PDDA/SiW12 (b-1), CNTs-PDDA/PMo12 (b-2), and CNTs-PDDA/P2Mo18 (b-3).

1490

Y. Song et al. / Materials Research Bulletin 42 (2007) 14851491

Fig. 4. Cyclic voltammograms of CNTs (a); CNTs-PDDA/SiW12 (b-1), CNTs-PDDA/PMo12 (b-2), and CNTs-PDDA/P2Mo18 (b-3).

CNTs (a) and CNTs-PDDA/POMs (b) nanocomposites. It can be seen from Fig. 4(a) that in the potential range 400 to +400 mV (versus SCE), there is no redox peak at the working electrode. While at the SiW12-functionalized carbon nanotubes working electrode, three reversible redox peaks appear and the formal potentials E1/2 = (Epa + Epc)/2 for the three pairs of peaks are 0.16, 0.44, 0.77 V in 1 M CH3COOH1 M CH3COONa buffer at scan rate = 10 mV/s, as shown in Fig. 4(b)-1. Furthermore, Fig. 4(b)-2 shows three waves of CNTs-PDDA/PMo12 at +0.27, +0.12, 0.11 V when scanned in 0.05 M H2SO4 at 5 mV/s. When P2Mo18-functionalized nanocomposites were scanned in 0.5 M H2SO4 solution at scan rate of 5 mV/s, three redox waves were observed at +0.42, +0.33, +0.16 V in Fig. 4(b)-3. All of the wave formal potential values of three POMs are similar to the literature [21]. The above experimental results attest to the successful fabrication of CNTs-PDDA/POMs nanocomposites. Considering that POMs have excellent electrocatalysis properties and meanwhile CNTs can probably be used as active and stable catalysts for certain reactions [23], the obtained nanocomposites may have potential applications in electrocatalytic elds.

4. Conclusion In summary, we have showed a facile strategy through noncovalent functionalization of CNTs with Keggin and Dawson type POMs. The experimental results presented in this paper demonstrated that the basic structure and electrochemical activity of POMs are maintained in the nanocomposites. Furthermore, the electrochemical properties

Y. Song et al. / Materials Research Bulletin 42 (2007) 14851491

1491

of CNTs are enhanced when they are functionalized. The electroactivity of the nanocomposites are envisaged to make them very useful for basic electrochemical studies. Acknowledgment Financial support for this work was provided by the National Natural Science Foundation of China (Grant 20371011). References
[1] [2] [3] [4] L.N. Lewis, Chem. Rev. 93 (1993) 2693. B.L. Cushing, V.L. Kolesnichenko, C. OConnor, J. Rev. Chem. 104 (2003) 3893. K. Balasubramanian, M. Burghard, Small 1 (2005) 180. (a) A. Dawson, P.V. Kamat, J. Phys. Chem. B 105 (2001) 960; (b) C. Pacholski, A. Kornoeski, H. Weller, Angew. Chem. Int. Ed. 43 (2004) 4774; (c) V. Subramaniam, E. Wolf, P.V. Kamat, J. Phys. Chem. B 105 (2001) 11439. S. Iijima, Nature 354 (1991) 56. (a) M. Ouyang, J.-L. Huang, C.M. Lieber, Acc. Chem. Res. 35 (2002) 1018; (b) P. Avouris, Acc. Chem. Res. 35 (2002) 1026. (a) K.P. Gong, Y.M. Yan, M.N. Zhang, L.Q. Mao, Anal. Sci. 21 (2005) 1383; gl, Angew. Chem. Int. Ed. 40 (2001) 2066; (b) G. Mestl, N.I. Maksimova, N. Keller, V.V. Roddatis, R. Schlo (c) P. Serp, M. Corrias, P. Kalck, Appl. Catal. A: Gen. 253 (2003) 337. guin, A. Kuhn, M.-H. Delville, Electrochim. Acta 51 (2006) 2373; (a) P.J. Kulesza, M. Skunik, E. Frackowiak, F. Be (b) M.A. Correa-Duarte, M. Grzelczak, J. Phys. Chem. B 109 (2005) 19060; (c) D.M. Guldi, G.M.A. Rahman, N. Jux, D. Balbinot, J. Am. Chem. Soc. 127 (2005) 9830; (d) K.A. Shiral Fernando, Y. Lin, W. Wang, S. Kumar, Y.P. Sun, J. Am. Chem. Soc. 126 (2004) 10234; (e) Y.Y. Liu, J. Tang, J.H. Xin, Carbon 44 (2006) 381. ller, Polyoxometalates: From Platonic Solid to Anti-Retroviral Activity, Kluwer Academic Publishing, Dordrecht, 1994. M.T. Pope, A. Mu hwald, D. Volkmer, D.G. Kurth, Langmuir 22 (2006) 1949; (a) S.Q. Liu, H. Mo (b) Z.H. Chen, Y. Ma, J.N. Yao, New J. Chem. 26 (2002) 621; (c) L. Gao, E.B. Wang, Z.H. Kang, Y.L. Song, J. Phys. Chem. B 109 (2005) 16587. M. Sadakane, E. Steckhan, Chem. Rev. 98 (1998) 219. D.W. Pan, J.H. Chen, W.Y. Tao, Langmuir 22 (2006) 5872. (a) M. Filowitz, R.K.C. Ho, W.G. Klemperer, Inorg. Chem. 18 (1979) 93; (b) C. Rocchiccioli-Deltcheff, M. Fournier, R. Frank, R. Thouvenot, Inorg. Chem. 22 (1983) 207; (c) H. Wu, J. Biol. Chem. 43 (1920) 189. B. Kim, W.M. Sigmund, Langmuir 20 (2004) 8239. tter, D. Volkmer, J. Am. Chem. Soc. 124 (2002) 12279. S.Q. Liu, D.G. Kurth, B. Bredenko H. Paloniemi, M. Lukkarinen, Langmuir 22 (2006) 74. G. Decher, J.D. Hong, Ber. Bunsenges. Phys. Chem. 95 (1991) 1430. G.H. Jiang, L. Wang, C. Chen, Mater. Lett. 59 (2005) 2085. M.N. Zhang, L. Su, L.Q. Mao, Carbon 44 (2006) 276. J.G. Wu, Scientic and Technical Documents Publishing House, Technology and Applications of Fourier Transform Infrared Spectroscopy, 1994, vol. 1, p. 615. (a) T. Okuhara, N. Mizuno, M. Misono, Adv. Catal. 41 (1996) 113; (b) W.G. Klemperer, Inorg. Synth. Chapter Three: Early Transition Metal Polyoxoanions, 1992. X.L. Wang, E.B. Wang, Y. Lan, Electroanalysis 14 (2004) 1116. (a) N. Muradov, Catal. Commun. 2 (2001) 89; (b) Z.H. Kang, E.B. Wang, B.D. Mao, Appl. Catal. A: Gen. 299 (2006) 212.

[5] [6] [7]

[8]

[9] [10]

[11] [12] [13]

[14] [15] [16] [17] [18] [19] [20] [21] [22] [23]