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High Dispersion and Electrocatalytic Properties of Platinum on Functional Multi-Walled Carbon Nanotubes
Dao-Jun Guo, Hu-Lin Li*
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, P.R. China State Key Laboratory of Applied Organic Chemistry, Lanzhou 730000, P.R. China *e-mail: lihl@lzu.edu.cn Received: June 28, 2004 Final version: September 28, 2004 Abstract Platinum (Pt) nanoparticles were electrochemically dispersed on 4-aminobenzene monolayer-grafted multi-walled carbon nanotubes (MWNTs) by a potential-step method. The structure and nature of the resulting Pt-MWNT composites were characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The electrocatalytic properties of Pt-MWNT composites for methanol oxidation have been investigated by cyclic voltammetry (CV) and high electrocatalytic activity can be observed. This may be attributed to the small particle size, high dispersion of platinum particles and the particular properties of MWNT supports. The results imply that the PtMWNT composites have good potential applications in direct methanol fuel cell (DMFC). Additionally, the long-term cycling stability of platinum catalysts was also investigated. Keywords: Platinum nanoparticles, MWNTs, Electrocatalysis, Methanol, 4-Aminobenzene monolayer

1. Introduction
Carbon nanotubes (CNTs), as a new form of carbon, have become the focus of current research due to their special mechanical and electronic properties [1 4]. Attaching metal nanoparticles to carbon nanotubes and nanotube sidewalls is of interest to obtain nanotube/nanoparticle hybrid materials with useful properties [5]. The metallic particles with electrocatalytic activity may decorate the external walls of the nanotubes [6]. Since CNTs are chemically inert, activating their surfaces is an essential prerequisite for linking nanoparticles to them [7]. Chemical treatments are common methods to generate acid groups on CNTs [8]. However, previous attempts to prepare metal nanoparticles on carbon nanotube surface have not often obtained size-similar and highly dispersed nanoparticles. One of the reasons is that metal nanoparticles are spontaneously formed at the defect sites on the surface of carbon nanotubes. Therefore to obtain a good highly dispersed nanoparticles, the spontaneous deposition of metal nanoparticles on carbon nanotube must be suppressed. For example, Yu et al. [9] obtained a well-dispersed deposition of Pt clusters on the surface of CNTs via acid groups as specific nucleation sites. Jiang et al. [10] attached highly dispersed Au nanoparticles to carbon nanotubes through various modifications using cationic polyethyleneamine or anionic citric acid as the dispersant. In this paper, a novel method has been described for preparation of Pt nanoparticles through molecule-level design, analogous to the procedure employed to disperse Pt particles on other carbon substrates such as highly oriented pyrolytic graphite (HOPG) in the literature [11] as shown in
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Fig. 1. First, an ordered 4-aminobenzene monolayer was grafted onto the MWNT surface by electro-reduction of 4nitrobenzenediazonium tetrafluoroborate according to oth er work [12 19]; then PtCl 2 were adsorbed onto the 6 modified MWNT surface by electrostatic interaction; finally, Pt nanoparticles could be obtained through pulsed potentiostatic reduction. Modifying a 4-aminobenzene monolayer on a MWNT surface has several advantages. (1) The 4-aminobenzene group is modified on a MWNT surface via a CC covalent bond which is strong and suitable as substrate for nanoparticles deposition. (2) Covalent bonding of two-dimensional 4-aminobenzene on MWNT surfaces provides a uniform functional surface, which can effectively prevent the preferred nucleation process on the MWNT surface. (3) The specific electrostatic interaction between the substrate and adsorbed atom can cause particle

Fig. 1. Schematic procedure for the preparation of dispersion of Pt on MWNT surface.

DOI: 10.1002/elan.200403164

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870 size distributions to be considerably narrower than in the case of random nucleation [20]. (4) This technology provides the improved protection of metal nanoparticles with minimal surface deactivation.

D.-J. Guo, H.-L. Li

nanoparticles modified carbon nanotubes ethanol solution on the carbon-coated Cu grids and observed in the electric pressure of 100 kV. X-ray diffraction (XRD) data of the samples were collected using a Rigaku D/MAX 24000 diffractmeter with Cu-Ka radiation.

2. Experimental 3. Results and Discussion

2.1. Preparation of Carbon Nanotube Paste (CNTP) Electrodes MWNTs were produced via the chemical vapor deposition method [21]. The as-produced samples were purified by procedures already reported in the literature [21, 22]. Carbon nanotubes paste electrodes were prepared by mixing single-walled carbon nanotubes and mineral oil in a ratio 60.0% W/W nanotubes powder and 40.0% W/W mineral oil. The paste was carefully hand-mixed in a mortar and then packed into a cavity (3-mm diameter, 2-mm depth) at the end of a Teflon tube. The electrical contact was provided by a copper wire connected to the paste in the inner hole of the tube. The paste was kept at room temperature in a desiccator until used. 3.1. Covalent Modification of MWNTs with 4-Aminobenzene Figure 2 shows cyclic voltammograms of 2.0 mM 4-nitrobenzenediazonium tetrafluoroborate in 0.1 M H2SO4 on a MWNT electrode at 5 mV/s. The cyclic voltammetry of 4nitrobenzenediazonium tetrafluoroborate in 0.1 M H2SO4 presents a broad irreversible wave (A) located at 0.4 V(vs. SCE) which is attributed to the formation of the 4-nitrobenzene radical form the diazonium derivative [28, 29], this first one-electron wave is immediately followed by a second irreversible six-electron wave (B) located at Ep 0.1 V(vs. SCE) which corresponds to the reduction of the nitro group into an amino group [15]. On the second cycle, the waves disappears, this indicates the formation of a coating on the electrode surface. This possibility on carbon substrate had been examined by XPS analysis in other works [19].

2.2. Modification Procedure The electrochemical modification of a MWNT electrode was performed in 0.1 M H2SO4 solution in the presence of 2.0mM 4-nitrobenzenediazonium tetrafluoroborate by scanning between 1.1 and 0.3 V (vs. SCE). After modified with 4-aminobenzene, the electrode was successively rinsed with 0.1 M H2SO4 and Milli-Q water to remove the physically adsorbed materials. The MWNT electrode was then immersed into 0.1 M HClO4 solution containing 1.5 mM PtCl 2 6 solution for several minutes. After being rinsed with 0.1 M HClO4, a PtCl 2 6 -adsorbed MWNT paste electrode was transferred to a 0.1 M HCl blank solution and platinum nanoparticles were grown on the 4-aminobenzene monolayer-grafted MWNT electrode by a pulsed potentiostatic method. The potential was stepped from 700 to 300 mV (vs. SCE) for 100 ms and returned to 700 mV.

3.2. Preparation of Pt Nanoparticles on the Modified MWNT Surface The potentiostatic deposition of platinum nanoparticles on the 4-aminobenzene monolayer-modified MWNTs was carried out by potential pulse from the rest potential of 0.70 V to 0.30 V for duration of 100 ms. A typical current time transient seen for PtCl 2 6 anions on a 4-aminobenzene monolayer-modified MWNTs in the 0.1 M HCl solution is shown in Figure 3. Curves A and B represent the transients of two contrasting electrodes in 0.1 M HCl solution: one is a

2.3. Measurements A conventional cell with a three-electrode configuration was used throughout this work. A CNTP working electrode was employed. A platinum foil served as the counter electrode and a saturated calomel electrode (SCE) was used as the reference electrode. Electrochemical measurements were performed with BAS100B electrochemical analyzer, and the potentials were measured and reported with respect to the SCE. The morphology of synthesized nanoparticles was observed on a Hitachi600 transmission electron microscopy (TEM). The samples were prepared by dropping the Pt
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Fig. 2. Cyclic voltammetry of 2.0 mM 4-nitrobenzenediazonium tetrafluoroborate in 0.1 M H2SO4 at a MWNT paste electrode. Scan rate: 5 mV/s.
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Platinum on Functional Multi-Walled Carbon Nanotubes

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Fig. 3. Typical current-time transient PtCl 2 6 anions grafted onto the 4-aminobenzene group-modified MWNTs in 0.1 M HCl.

Fig. 4. Transmission electron micrograph (TEM) image of 4aminobenzene monolayer modified MWNT (a) and Pt-MWNT composites (b).

4-aminobenzene monolayer-modified MWNT electrode without PtCl 2 6 anions pre-adsorption and the other is a 4aminobenzene monolayer-modified MWNTs electrode with PtCl 2 6 anions. Compared with these transients, curve B exhibits a much larger current, which clearly shows that PtCl 2 6 has been coordinated and reduced on the 4-aminobenzene monolayer-modified MWNT surfaces.

3.3. TEM Analysis of Pt-MWNT Composites The direct evidence of the formation of Pt nanoparticles on the surface of MWNTs was given by TEM (Fig. 4b.). Clearly, the surface of MWNTs was uniformly covered with a certain amount of platinum nanoparticles with an average size of 1 3 nm. Previous attempts to prepare platinum nanoparticles on carbon nanotube surface and/or other carbon substrate have not often obtained size-similar and highly dispersed platinum nanoparticles. One of the reasons is that platinum nanoparticles are spontaneously formed at the defects on the surface of carbon nanotubes. Therefore, to obtain a good particle size monodispersity, we protect MWNT surfaces through molecule-level design. Covalent bonding of a two-dimensional 4-aminobenzene monolayer on MWNT surfaces provides a uniform surface with positively charged sites which not only prevents the electroless deposition of platinum nanoparticles but also serves as a charge bridge for binding PtCl 2 6 anions [11], so Pt nanoparticles show no tendency to aggregate at steps or defects on the surfaces of MWNTs.

Fig. 5. Powder X-ray diffraction (XRD) pattern of Pt-MWNT composites.

46.28, 67.48 and 81.28 can be assigned to (111), (200), (220) and (311) crystalline plane diffraction peaks, respectively. The average size of the Pt particles is 2.6 nm calculated by the Scherrer formula, in good agreement with the results by the TEM image.

3.5. Electrochemical Properties of Pt-MWNT Composites Figure 6 shows the typical cyclic voltammograms of a 4aminobenzene grafted MWNT paste electrode and Pt/4aninobenzene grafted MWNT paste electrode in 0.5 M CH3 OH 0.5 M H2SO4 aqueous solutions, no current peaks of methanol oxidation are observed from curve (B) in Figure 6, which indicates that the 4-aminobenzene grafted MWNT electrode have no electrocatalytic activity for methanol oxidation. From curve (A) in Figure 6, two peaks of methanol oxidation can be observed and the peak potentials (Ep) are 0.75 and 0.5 V, respectively. The shape of the CV curves and the peak potential (Ep) are in accordant with other work [25].
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3.4. XRD Analysis of Pt-MWNT Composites X-ray power diffraction (XRD) spectrum of Pt-MWNT composites is shown in Figure 5. All peaks can be indexed as the Pt face-centered cubic (fcc) phase base on the data of the JCPDS file [23]. While the MWNTs showed typical peak of (002) phase of MWNTs or graphite [24]. The peaks at 39.78,
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electrode for methanol oxidation have been investigated and high electrocatalytic activity is observed. This may be attributed to the high dispersion of nanoscale platinum catalysts and the particular properties of carbon nanotubes. This simple and green nanoparticle deposition technique is not limited to Pd; it may be used to prepare a variety of metal nanoparticles on MWNT surfaces for catalysis applications.

5. References
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Fig. 6. The cyclic voltammograms of MWNT (A), Pt/MWNT (B) paste electrodes at 100 mV/s in 0.5 M H2SO4 0.5 M CH3OH.

Fig. 7. Long-term stability of Pt-SWNT composites in 0.5 M CH3OH 0.5 M H2SO4. Scan rate is 100 mV/s.

3.6. Long-Term Stability of Pt-MWNT Composite The long-term stability of Pt-MWNT composites was also investigated in 0.5 M CH3OH 0.5 MH2SO4 solutions. The results are shown in Figure 7, it can be observed that the peak current density decreases gradually with the successive scans. The loss of catalytic activity may result from the consumption of methanol during the CV scan. It also may be due to poisoning and the structure change of the platinum nanoparticles and a result of the perturbation of the potentials during the scanning in aqueous solutions, especially in the presence of the organic compound [26]. From Figure 7, we can see that the Pt/MWNTelectrode have good long-term stability.

4. Conclusions
Highly dispersed platinum nanoparticles are electrodeposited by potential-step method on 4-aminobenzene grafted MWNTs. The electrocatalytic properties of Pt/MWNT

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