In the Laboratory

Determination of the Real Surface Area of Pt Electrodes by Hydrogen Adsorption Using Cyclic Voltammetry
Jos M. Doa Rodrguez,* Jos Alberto Herrera Melin, and Jess Prez Pea Departamento de Qumica, Universidad de Las Palmas de Gran Canaria, Islas Canarias, Spain; *jose.dona@quimica.ulpgc.es

One of the most important parameters in heterogeneous catalysis, especially in electrocatalysis, is the real surface area of the catalyst or electrode, which will determine the catalyst activity (1). The electrocatalysis mechanism is based on the electrodeelectroactive species charge transfer through the electrode surface. So the reaction rate, and consequently the electric current, is proportional to the electrode real surface area. The human eye is not able to observe an electrodes microtopography. As a result, surface area measuring instruments designed for macroscopic systems can determine only the electrodes geometric surface area, not the real surface area involved in microscopic processes. Figure 1 shows different surface images depending on the observation scale. From a macroscopic viewpoint the electrode surface may appear perfectly flat, but the presence of surface steps, holes, kinks, and terraces yields a real surface area that is larger than the apparent one. To measure an electrode real surface area we need to use a microscopic probe. One such probe is the adsorption of gaseous atoms or molecules onto the solid surface. A gas molecule may be adsorbed on a solid surface by weak interactions (physisorption) or by strong interactions (chemisorption) (2). If physisorption takes place, the gas particles carpet the electrode surface forming a monolayer on which successive gas layers may adsorb (Fig. 2a). In this case the real surface area can be evaluated by measuring the amount of adsorbed gas and the area occupied by each gas atom or molecule. Then the real surface area (Sr) can be calculated as Sr = na NA aa (1) where na is the amount (in moles) of gas adsorbed in the monolayer, NA is Avogadros number, and aa is the area occupied by each adsorbed particle. When the gas is absorbed by chemisorption, each atom or molecule of gas is attached by a real covalent bond to an adsorption site. In the case of a metallic surface this adsorption site is an atom (Fig. 2b). The evaluation of the real surface area requires the determination of both the amount of adsorbed gas and the surface atom density of the theoretically flat metal from crystallographic data. Sr can be calculated as

10 mm

10 m

10 nm

Figure 1. Differences in detail of solid surface images depending on the order of magnitude of the measurement.

aa

Figures 2. Different adsorbate particles packaging in (a) physisorption and (b) chemisorption processes.

Sr =

na NA dm

physical chemistry and physicochemical techniques is required for good comprehension of this experiment. The experiment has been used in a course on physicochemical techniques for students of marine sciences. Students have previously taken several courses in physics (e.g., General Physics, Fluid Mechanics), chemistry (e.g., General Chemistry, Physical Chemistry, Organic Chemistry), and mathematics (e.g., Algebra, Calculus). But to perform this experiment, they only need basic concepts in general chemistry, electrochemistry, and mathematics. Experiment Fundamentals Hydrogen adsorption on the platinum electrode surface is achieved by application of sufficiently negative potentials to the electrode when this is in contact with an aqueous solution. Three regions may be distinguished in the cyclic voltammetric curve of a Pt electrode in contact with an acid solution (Fig. 3) (9). The oxygen region is found at positive potentials. During the positive sweep prior to O2 evolution, a hydrated Pt oxide monolayer is formed (anodic current).
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(2)

where dm is the surface metal atom density. In this paper we propose an easy experiment for physical chemistry, electrochemistry, chemical engineering, and analytical chemistry students, in which the real surface area of an electrode is determined by cyclic voltammetry. An explanation of this experiment can be found in ref 3. The theoretical basis and various applications of the cyclic voltammetry technique can be found in refs 49. Previous knowledge about general

JChemEd.chem.wisc.edu Vol. 77 No. 9 September 2000 Journal of Chemical Education

In the Laboratory

In the center of the voltammetric curve is a region where only low currents (positive anodic for the positive sweep and negative for the negative sweep) can be found. This is the double-layer region where only capacitive processes take place. Finally, the hydrogen region is found at negative potentials. This region will be studied in more detail. As more negative potentials are applied, the reduction of H+ and the adsorption of H atoms become stronger: H+(aq) + e + site H(ad) (3) This process continues as electrode potentials become more and more negative, until the formation of a H(ad) monolayer is achieved. Once the Pt surface is fully covered by hydrogen atoms, the adsorption of H2 molecules will take place: 2H(ad) H2(ad) (4) These adsorbed molecules come together to form hydrogen bubbles, that will leave the Pt electrode surface when they have grown large enough: nH2(ad) nH2(g) + 2n-sites (5) At this moment a high cathodic potential is applied on the electrode and many free sites are exposed to the solution. Immediately steps 3, 4, and 5 take place successively at a high rate, giving rise to the sharp cathodic current increase known as the hydrogen evolution. The formation of the H(ad) monolayer can be easily detected at the potential where the cathodic current rapidly rises. When the potential is reversed, the opposite processes (anodic currents in the hydrogen region) take place. This is a chemisorptive process and eq 2 can be used to calculate the Pt electrode real surface area. The value of dm can be evaluated using the Anderson criterion (10), which proposes that for aged polycrystalline surfaces, the lower Miller index planes (100), (110), and (111) predominate, in a proportion of 33% for each one. In this case for Pt, dm takes a value of 1.3 1015 cm 2 (11). Taking into account that this is a charge-transfer process in which the adsorption of a hydrogen atom on a Pt site involves one electron, the moles of adsorbed hydrogen atoms can be calculated as Q na = m (6) F where Qm is the charge associated with the formation of a monolayer and F is the Faraday constant. Then eq 2 can be rewritten as

where ti is the time when the hydrogen adsorption starts and tf is the moment when the monolayer is completed. For cyclic voltammetry the potential applied to the electrode in the negative sweep varies as V = V0 vt (10) where V0 is the initial potential, v is the potential sweep rate (dV /dt), and t is the time. Then

ti =
and

V0 Vi V0 Vf v , tf = v

(11)

dt = dV v
and eq 9 can be rewritten as:

(12)

Q=1 v

V 0V f / v

I dV
V 0V i / v

(13)

In this way, Qm can be calculated by integrating the voltammetric curves between the potentials where the cathodic current deviates from the double layer current and the hydrogen evolution starts. However, the capacitive current is not restricted to the capacitive region, but extends over the whole range of the electrode potential. For this reason Qm must be calculated as

Q=1 v

V 0V f / v V 0V i / v

I dV Q dl

(14)

where Qdl is the charge associated to double layer capacitive processes in the hydrogen adsorption region. The inset in Figure 3 shows the Qm and Qdl graphic evaluation.

20

Hydrogen region

Double layer region

Oxygen region

10

Current / A

Sr =

Q m NA Q m = F dm e dm

-10

(7)
-20

Hydrogen adsorption charge

where e is the electron charge. In this case, e dm = (1.602 10 19 C) (1.3 1015 cm 2) = 208 C/cm2. At this point, the main problem is the Qm calculation. Taking into account that dQ I= (8) dt then

Hydrogen evolution Double layer region

-600 -400 -200 0 200

Double layer capacitive charge

Hydrogen evolution charge

-30 -800

400

600

800

Potential / mV

Q=

tf ti

I dt

(9)

Figure 3. Cyclic voltammetric current potential curve for a platinum electrode in contact with a 0.5 M H2SO4 solution. The electrode potential is referenced to the mercury sulfate reference electrode (MSE). The inset shows the different charge contributions in the hydrogen region.

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In the Laboratory

The Experiment The experiment was performed in a thermostated threeelectrode cell (9) with a Hg/HgSO4/K2SO4(sat) reference electrode (MSE). Although the MSE reference electrode is not a common one, the use of more popular reference electrodes such as Ag/AgCl or Hg/Hg2Cl2 is not recommended because of possible Cl ion diffusion to the working electrode surface. The Cl ions, even at very low concentrations, strongly adsorb on the Pt electrode surface. This blocks the active surface sites and thereby masks the real electrode surface. On the other hand, the electrode potentials referenced to the MSE are easily converted to normal hydrogen electrode (NHE) referenced potentials by adding 640 mV. This kind of reference electrode is very safe under normal operating conditions. However, some safety rules must be observed in case of electrode breakage:
CAUTION: Mercury and mercury compounds are poisonous and teratogenic (12). If metallic mercury is spilled, a silver bar can be used to collect it and deposit it in a proper container. Positively charged metal ions can be removed from solution by using Amberlite IR-120(plus) or Dowex 50X8-100, strongly acid gel-type resins with a sulfonic acid functionality. Solutions of HgCl2 that contain negatively charged species can be decontaminated using Amberlite IRA-400(Cl) or Dowex 1X8-50 (13).

Once Qdl is subtracted from the calculated Q value, a value of about 62.5 C is obtained for Qm. By eq 7 we calculated an electrode real surface area of about 0.3 cm2, which is 50% higher than the 0.2 cm2 value of the geometric surface area. About 90% of the students obtained good agreement between their results and the expected ones (less than 10% difference). When erroneous results were obtained, students were questioned about the certainty of their values and asked to repeat the measurement once again. These cases illustrate the importance of performing the determination twice in triplicate. Conclusions Measuring the I/V voltammetric curves in aqueous solutions is an easy way to determine real surface area by hydrogen adsorption. Clearly, the real surface area differs highly from the geometric one, indicating the importance of electrode microtopography in processes that involve the electrode surface. This is clearly perceived by the students. Remarks Mercury is a very common electrode in polarographic and voltammetric experiments. It is well known that hydrogen and oxygen do not adsorb on mercury and this method is not suitable to determine the Hg electrode real surface area. However, as the mercury electrode is liquid, surface rugosities are not expected to be present. So in this case, the real surface area will coincide with the geometric one. Literature Cited
1. Smith, J. M. Chemical Engineering Kinetics, 3rd ed.; McGrawHill: New York, 1986; pp 383419. 2. Levine, I. N. Physical Chemistry, 3rd ed.; McGraw-Hill: New York, 1991; pp 417448. 3. Sawyer, D. T.; Sobkowiak, A.; Roberts, J. L. Electrochemistry for Chemists, 2nd ed.; Wiley: New York, 1995. 4. Maloy, J. T. J. Chem. Educ. 1983, 60, 285. 5. Reinmuth, W. H. Anal. Chem. 1960, 32, 1509. 6. Albahadily, F. N.; Mottola, H. A. J. Chem. Educ. 1986, 63, 271. 7. Ontko, R. J.; Russell, R. N.; Ongren, P. J. J. Chem. Educ. 1986, 63, 325. 8. Baldwin, R. P.; Ravichandran, K.; Johnson, R. K. J. Chem. Educ. 1984, 61, 820. 9. Bard, A. J.; Faulkner, L. R. Electrochemical Methods. Fundamentals and Applications; Wiley: New York, 1980. 10. Anderson, J. R. Structure of Metallic Catalysts; Academic: London, 1975. 11. Biegler, T.; Rand, D. A. J.; Woods, R. J. Electroanal. Chem. 1971, 29, 269. 12. Lewis, R. J. Sr. Saxs Dangerous Properties of Industrial Materials, 8th ed.; Van Nostrand Reinhold: New York, 1992; pp 21882204. 13. Lunn, G.; Sansone, E. B. Destruction of Hazardous Chemicals in the Laboratory, 2nd ed.; Wiley: New York, 1994; pp 235238. 14. Conway, B. E.; Angerstein-Kozlowska, H.; Sharp, W. B. A.; Criddle, E. E. Anal. Chem. 1973, 45, 1331.

The working electrode was a platinum sheet with a geometric surface area of 0.2 cm2 (taking into account both sides). The counter electrode was a platinum helical wire. The test solution was 0.5 M H2SO4, which was deaerated with N2 gas for 10 minutes before the experiment. A N2 flow was maintained over the solution to avoid air exchanges with the environment. The voltammetric experiment was carried out using a Princeton-Applied-Research Model 263 Potentiostat/ Galvanostat and the voltammetric curves were recorded using a Linseis LY 18100 recorder. The voltammetric curves were obtained at 25 C between 800 and 665 mV vs MSE, at a scan rate of 50 mV/s. Initially, continuous cyclic scans between the limits were applied to the electrode until a reproducible voltammetric curve was obtained (about 10 minutes). This treatment, called electrode activation, irreversibly oxidizes adsorbed organic impurities on the electrode surface. Sometimes the electrode activation is not able to eliminate hard-to-oxidize impurities. In this case it is necessary to extend the electrode potential sweep limit to more positive potentials during a couple of scans to ensure the complete elimination of impurities (14 ). In general, two hours is enough for the experiment, including the solution preparation and electrode activation. Results After successive scans are reproducible, one of them is recorded (Fig. 3) and Qm is determined by integrating the cathodic part of the hydrogen region. Many computer programs provide an easy way to treat and integrate these curves. In our case, the EG&G Headstart Creative Electrochemistry Software was used for both experiment control and the data treatment.

JChemEd.chem.wisc.edu Vol. 77 No. 9 September 2000 Journal of Chemical Education

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