ISSN 1023-1935, Russian Journal of Electrochemistry, 2009, Vol. 45, No. 7, pp. 731735. Pleiades Publishing, Ltd. 2009.

. Published in Russian in Elektrokhimiya, 2009, Vol. 45, No. 7, pp. 785790.

Ethanol Electrocatalytic Oxidation on Highly Dispersed PtTiO2/C Catalysts1

Bing Wua, b, Ruihai Cuic, Ying Gaob, and Zhaohua Jianga,z
a

Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001, PR China b Department of Chemistry, Harbin Normal University, Harbin 150080, PR China c Department of Chemistry, Harbin University, Harbin, 150080, P. R. China e-mail: jiangzhaohua_hit@163.com
Received May 14, 2007

AbstractCarbon supported PtTiO2 (PtTiO2/C) catalysts were prepared with colloidal and chemical reduction method on different conditions and used for ethanol electrooxidation in acidic solution. The size of TiO2 and Pt crystal varied on the catalysts prepared by different methods and the Electrochemical specic surface area (ESA) also showed different on these catalysts. The catalytic activity on these carbon supported PtTiO2 catalysts showed some different behaviors. Key words: titanium dioxide, direct alcohol fuel cell, ethanol electrooxidation, electrocatalytic, adsorbed CO DOI: 10.1134/S1023193509070039

1. INTRODUCTION Many efforts were made so as to nd alternative fuels for the direct methanol fuel cell in the view of the fact that methanol is toxic and inammable and also because it has high crossover effect, thereby impeding the cathode performance. Besides methanol, other small organic compounds such as formic acid [13], Ethanol [49], Acetaldehyde [10], ethylene glycol (EG) [11, 12], and other alcohols [13] have therefore been considered as alternatives. Among these fuels, ethanol is an interesting candidate for direct conversion into electrical energy in the direct alcohol fuel cell systems, mainly because alcohol is much less toxic, inexpensive and has less crossover effect than methanol and also it is a green fuel and can be readily and easily produced in great quantity by fermentation of sugar-containing raw materials. These possible alternative fuels, however, have the same problem of low catalytic activity and low kinetics at anode as methanol. Pt is a good catalyst for alcohol electro-oxidation, but it is very easy to be poisoned by CO, which is believed to be an intermediate of alcohol electrooxidation [14]. Bimetal and metal oxide catalysts such as PtRu [1517], PtSn [18], PtWOx [19, 20] and PtTiO2 [21] have been studied to enhance the catalyst activity and CO tolerance. Here in this paper carbon supported PtTiO2 catalysts prepared by colloid and chemical reduction method on different conditions were used as anode catalysts and rstly used for ethanol oxidation and compared the electrocatalytic oxidation activity of these catalysts for ethanol.
1 The article is published in the original. z Corresponding author: jiangzhaohua_hit@163.com

2. EXPERIMENTAL 2.1. Preparation of Carbon Supported Pt-TiO2 Catalysts and Electrodes 2.1.1. Colloidal titanium dioxide preparation Colloid 1: 43.6 l tetrabutyl titanate was added dropwise to 25 ml alcohol (ethanol : water = 5 : 1 by volume) in a beaker under constant stirring at room temperature and the mixture was adjusted to pH 7 by dilute nitric acid and the colloidal TiO2 was obtained. Colloid 2: 43.6 l tetrabutyl titanate was added dropwise to 25 ml alcohol (ethanol : water = 5 : 1 by volume) in a beaker under constant stirring at room temperature and the mixture was adjusted to pH 7 by glacial acetic acid and the colloidal TiO2 was obtained. Colloid 3: 43.6 l tetrabutyl titanate was added dropwise to 25 ml alcohol (ethanol : water = 5 : 1 by volume) in a beaker under constant stirring at room temperature and the mixture was adjusted to pH 7 by glacial acetic acid. Then 150 l methanol solution and polyethylene glycol mixture was added to make the mixture even transparent solution and the colloidal TiO2 was obtained. 2.1.2. Preparation of carbon supported PtTiO2 catalysts Firstly, the suspending liquid of ethylene glycol (25 ml) and Vulcan XC72R (0.19 g) activated carbon black (Cabot Co. from American) was obtained by agitating ultrasonically for 1 h and heating and stirring for 3 h in a bath thermostatically maintained at 80C.

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in the catalyst layer was about 1 mg cm2. The Electrode prepared from Cat.a, Cat.b, Cat.c were designated as PtTiO2/C-a, PtTiO2/C-b and PtTiO2/C-c correspondingly. 2.2. Electrochemical Measurements All the electrochemical measurements were performed on CHI650A electrochemical workstation. All chemicals used were analytical grade and all solutions were freshly prepared with triply distilled water. A three-electrode electrochemical cell equipped with the working electrode (the Pt/C electrode prepared), counter electrode (a platinum mesh) and a reference electrode (KCl-saturated AgAgCl) connected to the cell via a Luggin capillary was used. The electrolyte was 0.5 mol l1 H2SO4 solution with 1.0 mol l1 ethanol for ethanol electrooxidation. Before the electrochemical measurements, oxygen was purged with bubbling the highly puried N2 (99.999% from Nanya gas limited Company) for 20 min to get an anaerobic operating environment. In order to measure the electrochemical behavior of the adsorbed CO (Oad), CO (99.99% from Northeast special gas limited Company) was bubbled into the solution for 10 min and stewing for 10 min to allow complete adsorption of CO onto the catalysts. The excess CO dissolved in the electrolyte and in the gas phase above the electrolyte surface was purged out with highly puried N2 for at least 10 min. The Oad electrooxidation was carried out in 0.5 mol l1 H2SO4. Pretreatment of the electrodes were done before any electrochemical measurements by cyclic voltammetry in the potential range from 0.3 to 1.3 V at a sweep rate of 10 mV s1. Five cycles were enough to obtain reproducible electrode behavior. The electrochemical experiments were carried out at 25 and 60C and potential sweep rate is 10 mV s1. All potentials were given versus the reference KCl-saturated AgAgCl electrode. 3. RESULTS AND DISCUSSION 3.1. Analysis of the Particle Size and the Electrochemical Specic Surface Area The charges under the hydrogen adsorption/desorption peaks in 0.5 mol l1 H2SO4 acid background (Fig. 1) were used for roughly estimating the electrochemical specic surface area (SESA) by the following equation: 0.1 Q / k 2 1 -(m g ) . S = ---------------WL Where W is the weight of the catalyst (g), L the weight percent of platinum (wt %) and Q is the coulometry of hydrogen adsorption/desorption (mC). Here k = 210 C cm2 for hydrogen. The results are shown in table. The average diameter of platinum particle (assuming it has a spherical shape) can be calculated from the specic surface area by the equation: 6m -, d = ------------ S ESA
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Fig. 1. The linear sweeping curves of carbon supported Pt TiO2 (2 : 1 by atom) and Pt/C catalysts in 0.5 mol l1H2SO4 solution, scan rate: 10 mV s1, 25C. 1 Cat. a, 2 Cat. b, 3 Cat. c, 4 Pt/C.

Secondly, the colloids prepared in 2.1.1 were added to the suspending liquid, respectively, thoroughly stirred and aged for 72 h. And then the slurry was ltered and dried in the vacuum condition and the carbon supported TiO2 (TiO2/C) was obtained after heat treated at 400 in nitrogen for 2 h. Thirdly, TiO2/C obtained above was dispersed into glycol solvent by sonication and 6.8 ml H2PtCl6 (7.35mgPt/ml) was added dropwise under mechanical stirring for 1 h at 80C. Finally, excess HCOOH has been added to mixture to reduce H2PtCl6 to form Pt catalyst on the TiO2/C powder for 2 hours under magnetic stirring at pH 10 (the pH has been adjusted to 10 by the addition of NaOH to the solution). Then the PtTiO2/C catalysts were obtained. The Catalysts prepared from Colloid 1, 2, 3 were designated as Cat.a, Cat.b and Cat.c correspondingly. The catalyst prepared all contained 20 wt % Pt and the atom ratio is Pt : Ti = 2 : 1. For cooperation, Pt/C was also prepared according to Ref. [9]. 2.1.3. Preparation of carbon supported PtTiO2 electrodes 2.5 mg PtTiO2/C catalysts were dispersed in ethanol, 5% Naon and PTFE and agitated ultrasonically for 5 min, respectively. The slurries were spread on carbon paper with an exposed surface area of 0.5 cm2 and dried at the room temperature in the air. The Pt loading
The average diameter of Pt particle (d) and the specific surface area of Pt (SESA) PtTiO2/C Cat. a Cat. b Cat. c Pt/C d, nm 7.9 7.5 4.5 13.5 SESA, m2/g 35.52 37.27 61.95 20.77

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Fig. 2. The linear sweeping curves of the adsorbed CO electrooxidation at PtTiO2 (2 : 1 by atom)/C and Pt/C catalysts in 0.5 mol l1 H2SO4 solution, scan rate: 10 mV s1, 25C. (a) Cat. a, (b) Cat. b, (c) Cat. c, (d) Pt/C.

Fig. 3. The linear sweeping curves of the adsorbed CO electrooxidation at PtTiO2 (2 : 1 by atom)/C and Pt/C catalysts in 0.5 mol l1 H2SO4 solution, scan rate: 10 mV s1, 60C. (a) Cat. a, (b) Cat. b, (c) Cat. c, (d) Pt/C.

where m is mass of Pt, is platinum specic density (21.4 g cm3), SESA is true surface area of Pt measured by hydrogen adsorption. The results are also shown in table. It can be see from table that Cat.c has the biggest Electrochemical Specic Surface Area and the smallest mean particle size of Pt. 3.2. Electrochemical Characteristics of Adsorbed CO Oxidation The linear sweeping curves of the adsorbed CO electrooxidation on PtTiO2/ and Pt/C catalysts in 0.5 mol l1 H2SO4 solution at 25 are shown in Fig. 2. It is clear to see that the positive sweep peak potentials of the Cat.a, b, c are nearly the same, about 0.61 V, slightly positive than that of Pt/C. But the onset potential for Oad electrooxidation on Cat.c (0.48 V) appears more negative than that on Cat.a (0.55 V), Cat.b (0.53 V) and Pt/C (0.50 V). The positive scan peak current densities for Oad electrooxidation on the catalysts increase in the order of Pt/C < Cat.a < Cat.b < Cat.c. Figure 3 shows the linear sweeping curves of the adsorbed CO electrooxidation on PtTiO2 (2 : 1 by atom)/C and Pt/C catalysts in 0.5 mol l1 H2SO4 solution at 60. It is obvious that the positive scan peak current densities for Oad electrooxidation at this higher temperature is familiar with that at 25, but the positive sweep peak potentials of the catalysts signicantly shifted negatively, especially for Cat.c, the peak potentials appears at 0.46 V, shift negatively 180 mV compared to that at 25. That is increasing temperature can signicantly improve the electrocatalytic activity of Oad and it is that the peak potential of Oad oxidation is sensitive to the temperature, but not the peak current density. Among the catalysts, the Cat.c has the highest electrocatalytic activity for COad not only at 25, but 60. This is mainly because more Pt exposed on the surface of electrode after adding the non-ionic surfactant polyethylene glycol during the preparation of Cat.c, increasing the activity sites and adsorptive capacity of
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CO and therefore enhancing the electrocatalytic activity of ethanol oxidation. 3.3. Electrochemical Characteristics of Ethanol Oxidation The ethanol Cyclic Voltammograms results on the three PtTiO2 (2 : 1 by atom)/C and Pt/C catalysts with a platinum loading of 1 mg cm2 at 25 in 0.5 mol l1 H2SO4 solution containing 0.5 mol l1 C2H5OH are reported in Fig. 4. We can see from Fig. 4 that the positive sweep peak potentials of ethanol on Cat.a, Cat. B, Cat.c and Pt/C are at 0.92, 1.00, 0.89 and 0.86 V, respectively. The peak potentials of ethanol on Cat.a, Cat.c and Pt/C are nearly the same, but the positive scan peak current density for ethanol electrooxidation on Cat.c (181.5 mA cm2) is much higher than that on Cat.a (115.9 mA cm2) and Pt/C(110.2 mA cm2), about 1.6 times higher. It can be also seen from Fig. 4 that although the peak current density for ethanol electrooxidation on Cat.c and Cat.b is close to each other, the peak potential of ethanol on Cat.c is shifting negatively by about 110 mV compared to Cat.b. Figure 5 shows the Linear sweep voltammograms of C2H5OH electrooxidation from 0.2 V to 0.8 V at Pt/C and PtTiO2 (2 : 1 by atom)/C catalysts prepared from different methods in the solution of 0.5 mol l1 C2H5OH + 0.5 mol l1 H2SO4 at 25C. It is obvious that the ethanol electrooxidation on the catalysts starts at nearly the same potentials, but the increasing gradient is bigger for Cat.c than that for the other three catalysts. The increasing degree order is Cat.c > Cat.b > Cat.a > Pt/C. And it can also be found in Fig. 5 that new shoulder peaks appear at potential 0.58 V on all the PtTiO2 (2 : 1 by atom)/C catalysts, especially obvious on Cat.c. And the current densities of the new shoulder peaks for Cat.a, Cat.b and Cat.c is 41.63, 52.28 and 55.32 mA cm2, respectively. But there is no new peak appearance at this potential on Pt/C. It seems that there is another active site on the surface of the catalysts. The involvement of TiO2 changes the electrochemical charNo. 7 2009

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Fig. 4. Cyclic Voltammograms of C2H5OH electrooxidation at PtTiO2 (2 : 1 by atom)/C and Pt/C catalysts in 1 mol l1 C2H5OH + 0.5 mol l1 H2SO4 solution, scan rate: 10 mV s1, 25C. 1 Cat. a, 2 Cat. b, 3 Cat. c, 4 Pt/C.

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Fig. 5. Linear sweep voltammograms of C2H5OH electrooxidation at PtTiO2 (2 : 1 by atom)/C and Pt/C catalysts in 0.5 mol l1 C2H5OH + 0.5 mol l1 H2SO4 solution, scan rate: 10 mV s1, 25C. (a) Cat. a, (b) Cat. b, (c) Cat. c, (d) Pt/C.

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acteristics of the catalysts. From the point of view of current density, threshold potential and peak position, Cat.c is thought to have the highest electrocatalytic activity for ethanol electro-oxidation among the catalysts investigated here. This is probably because that Cat.c has the biggest electrochemical specic surface area than those of Cat.a, Cat.b and Pt/C and this makes highly dispersed TiO2 supply more oxidized spices for ethanol oxidation on Cat.c. Comparing the preparations of Cat.a, Cat.b and Cat.c, for the non-ionic surfactant polyethylene glycol was added during the preparation of Cat.c, the colloidal TiO2 was covered and encapsulated by polyethylene glycol, making spatial steric hindrance. The shielding effect created by the macromolecular lm slightly decreases the Zeta potential of the colloidal and it makes the colloidal in a uniform dispersion state [224] and makes more Pt exposed on the surface of the electrode and therefore enhances the electrocatalytic activity of ethanol oxidation on Cat.c. It can be concluded from the results that, within the nanoparticle size, the electrooxidation activity of the catalysts mainly depends on electrochemical specic surface area and the particle size. Figure 6 shows the ethanol Cyclic Voltammograms results on PtTiO2 (2 : 1 by atom)/C and Pt/C catalysts with a platinum loading of 1 mg cm2 at 60C in 0.5 mol l1 H2SO4 solution containing 0.5 mol l1 C2H5OH. It can clearly be seen from Fig. 6 that the tendency of the onset potentials, the peak potentials and the peak current densities at 60C is the same with that at 25C, but the positive scan peak current densities for ethanol electrooxidation on the catalysts at 60C are much higher, about 2.4, 2.1, 2.8 and 3.2 times higher than that at 25C for Cat.a, Cat.b, Cat.c and Pt/C, respectively, but the peak potentials appear at higher potential at 60C than that at 25C. The results show that the order of electrocatalytic activity for ethanol oxidation is the same with that 25C, i.e. Cat.c > Cat.b > Cat.a > Pt/C. From the result one can see that, unlike COad oxidation, the peak potential of ethanol oxidation is sensitive to the temperature, and also the peak current density. 3.4. Chronoamperometry Figure 7 shows the chronoamperometry curves for Cat.a, Cat.b and Cat.c and the ethanol oxidation reaction which were biased at 0.8 V (versus AgAgCl) in the solution of 1.0 mol l1 C2H5OH and 0.5 mol l1 H2SO4 for 6000 s at 25C. After the steep dropping of initial current density with time, which believed to be the formation of COad and other intermediate species during ethanol oxidation [15], the current density decreased slowly. It can be seen from the gure that Cat.a has the highest stability among the catalysts, but lower current density than Cat.c. The current densities for Cat.a, Cat.b and Cat.c were 18.7, 16.8 and 27.5 mA cm2 after 2000s, respectively. So Cat.c has the highest current density and therefore has the highest electrocatalytic activity for ethanol oxidation.
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Fig. 6. Cyclic Voltammograms of C2H5OH electrooxidation at PtTiO2 (2 : 1 by atom)/C and Pt/C catalysts in 1 mol l1 C2H5OH + 0.5 mol l1H2SO4 solution, scan rate: 10 mVs1, 60C. (a) Cat. a, (b) Cat. b, (c) Cat. c, (d) Pt/C.

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0 0.2 2000 4000 6000 t, s

Fig. 7. The Amperometric it curves of C2H5OH at PtTiO (2 : 1 by atom)2/C catalysts in 1.0 mol l1 C2H5OH + 0.5 mol l1 H2SO4 solution, 25C, 0.8 V. 1 Cat. a, 2 Cat. b, 3 Cat. c.

4. CONCLUSIONS From the point of view of current density, threshold potential and peak position, the order of electrocatalytic activity for ethanol and COad electrooxidation among the catalysts investigated is Cat.a < Cat.b < Cat.c and are all more active than Pt/C in acidic solution. New peaks appear at lower potential for ethanol oxidation on all the PtTiO2 (2 : 1 by atom)/C catalysts because of the synergistic effect of TiO2. The increasing temperature can also improve the electrocatalytic activity of Pt TiO2 (2 : 1 by atom)/C catalysts for ethanol and COad electrooxidation. The results show that both the peak potential and the peak current density of ethanol oxidation is sensitive to the temperature, but only the peak potential of COad oxidation is sensitive to the temperature, not the peak current density. The particle sizes of Pt in the catalysts prepared here are all in nm scale. And the results show that the electrocatalytic activity of the catalysts for ethanol oxidation depends on electrochemical specic surface area or the particle size within the nanoparticle level. Among the catalysts, Cat.c has the highest electrochemical specic surface-area with the mean particle size 4.5 nm, which makes it possible to improve the electrocatalytic activity of ethanol and adsorbed CO oxidation. ACKNOWLEDGMENTS The authors thank the nancial support of the National Natural Science Foundation of China (no. 20573029), Natural Science Foundation of Heilongjiang Province (B200505) of China, the Fund of Department of Education of Heilongjiang Province (nos. 11531235, 11531243) of China and the Youth fund of Harbin Science and Technology Bureau (2007 RFQXG 079).

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