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Chemical Physics Letters 376 (2003) 130135 www.elsevier.


Probing dierent adsorption behavior of CO on Pt at solid/liquid and solid/gas interfaces by Raman spectroscopy with a three-phase Raman cell
Bin Ren


, Li Cui a, Xu-Feng Lin b, Zhong-Qun Tian


a Department of Chemistry, Xiamen University, Xiamen 361005, China State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005, China

Received 13 February 2003; in nal form 21 May 2003 Published online: 27 June 2003

Abstract A Raman cell suitable for the study of solid/liquid/gas three-phase systems and that can work very eciently on confocal microprobe Raman systems was introduced. The inuence of the environment on the adsorption behavior of model molecule CO on Pt was investigated and dierent behaviors were observed in the aqueous solution compared to the gas phase. A preliminary Raman measurement on the three-phase system was performed using methanol as a testing solution. The diusion of CO, a dissociate product of methanol, on the Pt electrode from the solution side to the gas side was observed. 2003 Elsevier Science B.V. All rights reserved.

1. Introduction Electrocatalysis is an interdisciplinary eld of electrochemistry and catalysis [13]. Electrochemistry is based on the modulation of electric signal (potential or current), which is able to modify the activation energy of the reaction system by simply changing the electric eld across the interface, therefore to change the reaction direction, rate and selectivity [4,5]. Catalysis mainly concentrates on the process occurring at the solid/gas interface,

Corresponding author. Fax: +86-592-2085349. E-mail addresses: (B. Ren), (Z.-Q. Tian).

normally by changing the temperature and pressure to control the reaction direction and rate [6]. In general, electrochemical process is much more complicate than ordinary catalytic one due to participation of various solvent and supporting electrolytes, and the eect of strong electric eld across the double layer [46]. In fact, many electrocatalysis-based systems such as fuel cells consist of two kinds of interfaces, solid/gas and solid/ liquid interfaces [7]. Therefore the situation becomes more complicate than normal electrochemical or catalytic systems. The adsorption and oxidation of carbon monoxide and hydrogen are typical and important systems in electrocatalytic processes, and have been widely studied in both electrochemistry and catalysis [7,8]. Various

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B. Ren et al. / Chemical Physics Letters 376 (2003) 130135


techniques, including electron and photon-based vibrational techniques have been applied to the study of adsorption and other interfacial processes occurring at the solid/liquid, solid/gas or liquid/gas interfaces [1013]. It was found that the adsorption behavior of CO or H on dierent substrates could be dierent and furthermore, that even for the same adsorbate on the same substrate but under dierent conditions, its behavior may be dierent [9,1418]. However, it should be pointed out that the above methods could only investigate at a certain interface. In order to understand the origin of the dierence, a derived approach, non-situ technique, was elaborated to bridge the gap, which works in a vacuum system by dosing dierent possible solvents and anions to simulate the condition of the solid/liquid interface [19,20]. However, the operation under the vacuum condition adds additional diculty to the method. Furthermore, the precise simulation is still a problem. In this study, we will present a specially designed Raman cell that can work under both catalytic and electrochemical control and allow the vibrational study of surface processes at both solid/gas and solution/liquid interfaces (three phases) simultaneously. Furthermore, by properly controlling the experimental condition one might be able to investigate the diusion process of a surface species between these two interfaces.

GFG-8016G function generator (Good Will Instrument, Co. Ltd.). Electrochemical cleaning of the electrode surface before and after roughening was controlled by a CHI631A electrochemical workstation (CH instruments, Inc.). The roughening procedure for a SERS-active Pt electrode has been reported elsewhere [21]. Two kinds of electrode were used in the present study. One was with an apparent surface area of 0.03 cm2 , which was easy to handle in the gas phase or the solid/liquid interface. A large platinum electrode with an apparent geometric area of ca. 0.78 cm2 was used for the three-phase system. Due to the slower electrochemical response of the large electrode, a square wave function with a lower frequency (ca. 600 Hz) was applied for the electrochemical roughening of the electrode. All other pretreatment to the electrode was the same as that described in Ref. [21]. The increment in the surface area with respect to the smooth surface was about 150. A large platinum ring served as the counter electrode. The reference electrode was a saturated calomel electrode (SCE), thus all the potentials in this Letter were quoted versus SCE. All the gases were of ultra-high grade purity, all the chemicals were of analytical reagents and the solutions were prepared using Milli-Q water.

3. Results and discussion 2. Experimental Raman spectra were acquired using a confocal microprobe Raman system (Labram I, Dilor). The excitation line was 632.8 nm from an internal He Ne laser. The laser was delivered on the sample through a long working distance microscopic objective with a magnication of 50 and the power on the sample was about 2.5 mW. Due to the special conguration of the three-phase cell, an adapter equipped with a mirror allowing the horizontal incidence of the laser was used before the objective. The applied current or potential during the roughening process and Raman measurements were controlled by a PAR 173 potentiostat (EG&G). Square-wave function was initiated by a A Raman cell of proper design is extremely important for the in situ three-phase study. Fig. 1a gives a view of the Raman cell under working condition. The reference electrode (1), counter electrode (2), gas inlet (3) and outlet (4) are mounted from the upper half surrounding the cell body. The cell is mounted to a cell holder (5) to make the working electrode face horizontally. With such a design, the cell can work with and without the solution or with a varied volume of solution and gas. An extremely important feature of the cell is the easy control of solution loading and gas exchange. In a case that the solution should cover the electrode under potential control, it can be lled into the cell from the inlet (3) by the introduction of a pipe, until the solution contacts both the reference and counter electrodes but not


B. Ren et al. / Chemical Physics Letters 376 (2003) 130135

Fig. 1. Diagram of the Raman cell to work in the three-phase study (a) and the small region between the electrode surface and the optical window was shown in (b). (1) Reference electrode, (2) counter electrode, (3) gas inlet, (4) gas outlet, (5) cell holder, (6) optical window, (7) working electrode, (8) solution, (9) gas phase and (10) laser.

the working electrode. Then the electrochemical potential control can be turned on. After that, more solution is lled until half of the surface area of the Pt working electrode was covered, which is used as a typical condition for the three-phase study. The upper half of the Pt surface remains intact during the solution loading process. The region between the working electrode and optical window under such a condition is enlarged and given in Fig. 1b. It can be seen that, when the electrode is covered partly by the solution (8) and the electrode (7) and window (6) spacing is not too thin (to prevent the capillary eect), a region of three phase will form. Therefore, when the cell is moved up and down relative to the laser (10), the signals from solid/liquid, solid/gas and solid/gas/ liquid interfaces can be detected. There are some reports on the design of spectroelectrochemical cells for UVVis, luminescence, infrared and SERS studies [2225]. However, there is no report for the study of a three-phase system. It should be pointed out that basically our design is not suitable for IR or SFG study even after the change of the window to material working in IR region because of the necessity of thick solution layer (about 1 mm) to avoid the capillary eect, which will cause severe absorption of the incident light and/or signal. On the other hand, for the investigation of electrocatalytic processes one has

to use a Pt-group substrate with SERS eect [2629]. Due to the very weak surface Raman signals from normal transition-metal surfaces we, in this study, will use the method developed in our group for preparing the SERS-active Pt electrode [21,2628] and combine the specially designed three-phase Raman cell to obtain the information from solid/liquid, solid/gas and solid/liquid/gas interfaces. In our previous study of the solid/gas systems, the property of the Rh surface was found to be signicantly inuenced by the composition of the gas phase [30]. Therefore, before starting the study of the three-phase system, it is also very important to rst investigate the surface property of the Pt electrode in dierent environments. The experiment was done without any solution in the Raman cell and the cell was rst exposed to air. It can be seen from the SERS spectrum in Fig. 2a that the major signal from the Pt surface is due to the Pt oxides centered at ca. 550 cm1 [26,31], no signal in other frequency region can be detected. It indicates that the Pt surface has been oxidized spontaneously in air. However, the oxidized Pt surface can be easily reduced by a H2 ow, see Fig. 2b. Besides the disappearance of the band related to Pt oxides, another new band centered at 2079 cm1 can be observed. This band comes from PtH vibration of

Fig. 2. Surface Raman signal from a Pt electrode in dierent gas environments: (a) air, (b) H2 and (c) O2 .

B. Ren et al. / Chemical Physics Letters 376 (2003) 130135


the a-top H according to our previous work in the electrochemical system [16]. However, the PtH can be easily removed by a ow of O2 gas, as evidenced by the disappearance of the PtH band and the re-emergence of the Pt oxides band, without the loss of the PtOx signal, see Fig. 2c. This study indicates that the Pt electrode is stable enough to retain the SERS activity after reduced by H2 and an oxygen-free Pt electrode for the investigation of surface process can be easily obtained by purging H2 . Since the main purpose of setting up this system is to have a better understanding of the electrocatalytic problems, we take the adsorption of CO in dierent environments to demonstrate the validity of the Raman cell to work in dierent environments. H2 gas was purged into the three-phase Raman cell for several minutes to reduce the Pt surface until no PtOx signal can be detected. Then, H2 gas ow was completely replaced by CO and the gas ow was maintained for ca. 7 min before the Raman measurement. Raman spectra acquired were shown in Fig. 3a with the CO pressure of ca. 1 atm in the cell. After that, the CO ow was switched to go through a bottle containing Milli-Q water mounted before the Raman

Fig. 3. Surface Raman spectra of CO obtained under dierent condition: (a) pure CO in the Raman cell, (b) purging CO through a bottle containing Milli-Q water to form a gas phase containing both CO and H2 O gas and (c) Milli-Q water saturated with CO without potential control over the electrode.

cell to obtain a gas phase containing both water vapor and CO gas. The Raman measurement was made also after ca. 7 min and the acquired spectra were showed in Fig. 3b. Finally, Milli-Q water saturated with CO was injected into the cell through its gas outlet (4) in Fig. 1 and the spectra acquired were showed in Fig. 3c. We did not nd obvious dierence between Figs. 3a and b obtained both under the condition of gas phase. They present nearly identical band features of the mPtC and mCO at 484 and 2072 cm1 , respectively [26,32]. It indicates that water vapor did not inuence the adsorption behavior of CO on the Pt surface. However, a blue shift of ca. 7 cm1 was observed in the mCO frequency in the surface Raman spectrum of CO in water (Fig. 3c) to that in the gas phase (Figs. 3a,b). A higher frequency may indicate a more compact structure of CO on the surface [17] or be due to the interaction of water hydrogen with the CO molecules. Since the adsorption of CO on Pt already reaches saturated adsorption in the gas phase, it seems the former may not be the reason. The above study reveals the dierent spectral feature for a same species in dierent environment and shows the possibility of Raman investigation in dierent interfaces in a same Raman cell. Furthermore, if the solution covers only part of the working electrode and we move the electrode cell along the vertical direction we will be able to monitor the process in gas/solid, gas/solid/liquid and solid/liquid interfaces and to compare the difference and similarity under three conditions, which will allow us to follow as close the condition as possible to the real reaction in electrocatalytic processes. In order to realize the measurement, the cell was mounted to a XY motorized stage with the electrode surface facing horizontally. The acidic methanol solution was lled in the cell until half of the working electrode was immersed. The experiment was done by moving the XY stage down while the focusing condition of the laser spot was monitored to allow the laser to focus in different phases in the cell, such as solid/liquid, solid/ liquid/gas and solid/gas interfaces. The main consideration of using 0.1 M methanol + 0.1 M H2 SO4 as the solution is: on the solution side, the methanol can dissociate on the Pt surface under potential


B. Ren et al. / Chemical Physics Letters 376 (2003) 130135

control [2,3], so we may be able to observe the product of adsorbed CO, on the other hand, in the gas phase, there is no such reaction. If one detects the signal of CO at the solid/gas interface, then it may be due to the surface diusion of CO on the Pt surface from solution side to the gas side. The result was given in Fig. 4. The top spectrum was obtained at the solid/liquid interfaces, and the second was acquired at the meniscus above the solution surface. According to what we observed in the monitoring camera, the third spectrum was possibly acquired at the edge of the meniscus, a condition of solid/liquid/gas interface. From this gure we can nd that the spectrum remains essentially the feature of the solid/liquid interface with intense signal of mPtC (due to the dissociation of methanol). However, one can nd that there is no signal from any solution species, probably because the liquid layer over the surface in the meniscus was too thin to give observable signal or there is no solution layer. However, when the laser is moved into the solid/gas interface, it is very interesting to observe that the signal from PtC signicantly decreases, and slightly red shifts, see the lower four spectra. In spite of no methanol in

the gas phase, there is still CO signal, though very weak. This indicates the existence of minor CO on the surface. One may argue that the appearance of CO may have two origins: one is by diusion (as described before) from the solid/liquid interface, and another possible reason could be the dissociation of the trace methanol in the gas phase due to the volatilization of methanol from the liquid phase into the gas phase. In order to verify the second assumption, we bubbled H2 into the methanol solution and let the gas ow through the cell. In this case, we did not detect any signal from PtC. This indicates that the CO on the surface came very possibly from the solid/liquid interface by surface diusion. With stronger signal after further optimization of the whole system and the preparation a better SERS active substrate, we may be able to investigate the diusion process occurring in the small region of three phases. The research along this avenue is now carried out in our lab.

4. Summary A Raman cell that can work under the conditions of both the solid/liquid interface with potential control and the solid/gas interface with a convenient gas ow control was introduced. This cell is further applicable to the solid/liquid/gas interfaces with convenient exchange of the solution and gas ow. For the investigation of the Pt group metals, special attention has to be paid to the oxidation of the surface. An oxygen-free Pt electrode can be conveniently obtained by purging the H2 gas into the cell for several minutes. An obvious dierence in the adsorption behavior of CO on the Pt electrode was found in the solution phase compared to the gas phase (with and without H2 O gas), the interaction of water hydrogen with CO was considered as the major reason. The rst Raman measurement concerning the three-phase system was done by using methanol as the testing solution. The sudden change in the spectra feature of CO while the laser focus is moved across the three-phase region revealed the diusion of CO on the Pt electrode from the solution side to the gas side.

Fig. 4. Surface Raman spectra obtained from a Pt surface by moving the laser illuminating spot from the solution to the gas phase. The solution is 0.1 M methanol + 0.1 M H2 SO4 . The potential of the electrode is controlled at )0.1 V.

B. Ren et al. / Chemical Physics Letters 376 (2003) 130135


Acknowledgements This work was supported by the Natural Science Foundation of China (Contract Nos. 29903009, 20021002 and 90206039).

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