Langmuir 2002, 18, 6274-6279

Surface-Enhanced Raman Spectroscopic Studies of Dissociative Adsorption of Amino Acids on Platinum and Gold Electrodes in Alkaline Solutions
Xiao-Yin Xiao,†,‡ Shi-Gang Sun,*,† Jian-Lin Yao,† Qi-Hui Wu,† and Zhong-Qun Tian†
State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, Xiamen University, Xiamen, 361005, People’s Republic of China, and Xiangtan Normal University, Xiangtan, 41110, People’s Republic of China Received April 9, 2002. In Final Form: May 23, 2002
The dissociative adsorption of amino acids on Pt and Au electrodes in 0.1 M NaOH solutions was studied by cyclic voltammetry and surface-enhanced Raman spectroscopy (SERS). The intermediate species has been determined as adsorbed cyanide, which is designated by a potential-dependent vibration band around 2110 cm-1 on both Pt and Au surfaces. The dissociation of glycine can be observed on Pt surface in a wide potential region to form cyanide, while the dissociation of serine and threonine occurs at relatively high potentials along with the oxidation of their functional groups. The onset potential of dissociation of amino acids on the Pt surface increases in the order glycine < threonine < serine. It has been revealed that the self-inhibition of amino acid oxidation is originated from the strongly adsorbed cyanide, which is oxidized at potentials above 0.2 V vs SCE. On gold surfaces, cyanide species can be formed only from anodic oxidation of amino acids. The present study reveals characteristic interactions between amino acid molecules and metallic electrode surfaces, as well as the role of amine group in the adsorption configuration.

Introduction The interaction of small organic molecules with electrode surface is a key step involved in electrocatalytic processes and has received extensive attention in studies concerning direct fuel cells.1 The most frequently employed electrocatalysts in direct fuel cells are platinum group metals and alloys.2 Infrared spectroscopy has played an important role in investigating the interaction of small organic molecules with Pt-based electrocatalysts,3-5 while Raman spectroscopy has less often been applied to such studies.6,7 This is because (1) highly reliable sensitivity of Raman spectral signal could be obtained only on roughened surfaces of coinage metals up to the end of the last century, and (2) low enhancement factors were found up to now only on rough platinum surfaces.8 However, surfaceenhanced Raman spectroscopy (SERS) is going forward with its capability of delivering specific chemical identification to more and more applications related to catalytic processes.6-8 Recent studies revealed the possibility of extending SERS on platinum surfaces to identifying molecules in the submonolayer range. Intermediate
* Corresponding author: Tel +86 592 2180181; fax +86 592 2183047; e-mail sgsun@xmu.edu.cn. † Xiamen University. ‡ Xiangtan Normal University.
(1) Sun, S. G. In Electrocatalysis; Frontiers of Electrochemistry Series, Vol. 4; Lipkowski, J., Ross, P. N., Eds.; Wiley-VCH: New York, 1998; Chapt. 6, pp 243-290. (2) Carrette, L.; Friedrich, K. A.; Stimming, U. Chem. Phys. Chem. 2000, 1, 162-193. (3) Wasmus, S.; Kuver, A. J. Electroanal. Chem. 1999, 461, 14-31. (4) Lin, W. F.; Wang, J. T.; Savinell, R. F. J. Electrochem. Soc. 1997, 144, 1917-1922. (5) Iwasita, T.; Hoster, H.; John-Anacker, A.; Lin, W. F.; Vielstich, W. Langmuir 2000, 16, 522-529. (6) Tian, Z. Q.; Gao, J. S.; Li, X. Q.; Ren, B.; Huang, Q. J.; Cai, W. B.; Liu, F. M.; Mao, B. W. J. Raman Spectrosc. 1998, 29, 703-711. (7) Mrozek, M. F.; Weaver, M. J. J. Am. Chem. Soc. 2000, 122, 150155. (8) Cai, W. B.; Ren, B.; Li, X. Q.; She, C. X.; Liu, F. M.; Cai, X. W.; Tian, Z. Q. Surf. Sci. 1998, 406, 9-22.

adsorbates from adsorption of small organic molecules, for example, methanol and ethylene, have been successfully examined by SERS.9-11 Amino acids contain different functional groups (-COOH, -OH, -NH2, -CHx, etc.) and provide the convenience to investigate the interaction of these functional groups with electrocatalytic surfaces. Their properties, and their adsorption characteristics as well, depend strongly on the acidity (pH value) of electrolyte.12,13 The weakly adsorbed species in acid media were examined as deprotonated amino acid molecules,14-17 of which the adsorption behavior was similar to those of their relative aliphatic acids (e.g., acetic acid).18,19 However, in alkaline media, Ogura et al.20-22 proposed the same weak adsorption model on Pt surface as that in acid media, which was in disagree(9) Ren, B.; Li, X. Q.; She, C. X.; Wu, D. Y.; Tian, Z. Q. Electrochim. Acta 2000, 46, 193-205. (10) Gu, R. A.; Cao, W. D.; Cao, P. G.; Sun, Y. H.; Yao, J. L.; Ren, B.; Tian, Z. Q. Acta Chim. Sin. 2001, 59, 356-359. (11) Mrozek, M. F.; Weaver, M. J. J. Phys. Chem. B 2001, 105, 89318937. (12) Horanyi, G.; Rizmayer, E. M. J. Electroanal. Chem. Interfacial Electrochem. 1986, 393-400. (13) Xiao, X. Y.; Sun, S. G.; Wu, Q. H.; Zhou, Z. Y.; Chen, S. P. Chem. J. Chin. University-Chin. 2000, 21, 1288-1292. (14) Huerta, F.; Morallon, E.; Cases, F.; Rodes, A.; Vazquez, J. L.; Aldaz, A. J. Electroanal. Chem. 1997, 421, 179-185. (15) Huerta, F.; Morallon, E.; Cases, F.; Rodes, A.; Vazquez, J. L.; Aldaz, A. J. Electroanal. Chem. 1997, 431, 269-275. (16) Huerta, F.; Morallon, E.; Vazquez, J. L.; Perez, J. M.; Aldaz, A. J. Electroanal. Chem. 1998, 445, 155-164. (17) Huerta, F.; Morallon, E.; Vazquez, J. L.; Aldaz, A. J. Electroanal. Chem. 1999, 475, 38-45. (18) Rodes, A.; Pastor, E.; Iwasita, T. J. Electroanal. Chem. 1994, 376, 109. (19) Pastor, E.; Rodes, A.; Iwasita, T. J. Electroanal. Chem. 1996, 404, 61. (20) Ogura, K.; Kobayashi, M.; Nakayama, M.; Miho, Y. J. Electroanal. Chem. 1998, 449, 101-109. (21) Ogura, K.; Kobayashi, M.; Nakayama, M.; Miho, Y. J. Electroanal. Chem. 1999, 463, 218-223. (22) Ogura, K.; Nakayama, M.; Nakaoka, K.; Nishihata, Y. J. Electroanal. Chem. 2000, 482, 32-39.

10.1021/la025817f CCC: $22.00 © 2002 American Chemical Society Published on Web 07/11/2002

No. Figure 1a shows the cyclic voltammogram of a Pt electrode in 0. and threonine [CH3CH(OH)CH(NH2)COOH] on platinum and gold electrode surfaces by SERS. 2002 6275 Figure 1.1 M NaOH solution.4 and -0.92 and 0. To see the dependence of the formation of poisonous species on electrode potential. -0. Experimental Section Raman spectra were obtained on a confocal microprobe Raman system (LabRam I).0 V.8 e. P. Amino acids of biochemical grade and sodium hydrate of analytical grade were used as received.8 nm from an air-cooled He-Ne laser that delivers a power of 10 mW at the sample point. Two pairs of oxidation/ reduction peaks at around -0.5 kHz with upper and lower potentials of 2.2 V at a scan rate of 0. c) solutions: (b) the first two cycles. because the adsorption of oxygen is inhibited.6 V. ultrasonically cleaned with triply distilled water. with a holographic notch filter and a CCD detector. and further blockage can be obtained by potential cycling between -0.1 M NaOH solutions containing threonine or serine. The electrode was then subjected to potential cycles between -0. the hydrogen adsorption is largely inhibited in comparison with a freshly prepared surface.25 and 1. such as glycine [CH2(NH2)COOH].92 V and then swept positively up to 0. -0.30 V is (23) Gao.1 M NaOH + 5 mM glycine (b. the voltammogram of the first two potential cycles of threonine at a Pt surface is shown in . we studied the adsorption and oxidation of amino acids with different configuration of R-group. 7122.30 V in the first anodic sweep.1 M NaOH solution after the adsorption. only one hydrogen desorption peak can be observed. The molecular and surface structural effects in the dissociative adsorption were investigated in a wide potential range from hydrogen adsorption potential region up to oxygen evolution.95 and 0. Chem.5 M H2SO4 for 5-10 min by applying a square wave of 1. (c) the steady profile. along with potential cycling in this potential region.Adsorption of Amino Acids on Pt and Au Electrodes Langmuir. Gosztola.8 Solutions were prepared from Millipore water and deaerated by nitrogen gas before immersion of the working electrodes. and -0. either the adsorption state was checked in the same solution containing 5 mM glycine or the electrode was transferred into 0.3 and 0. in which the hydrogen adsorption and glycine oxidation are close to fully inhibited.1 M NaOH (a) and 0. A large decrease of the oxidation current is observed in the subsequent potential sweep.1 M NaOH + 5 mM glycine solution at open circuit: In this case. The results show that the hydrogen adsorption is strongly inhibited in the first potential cycle.6 V. since we cannot observe such a large oxidation current in the case of glycine.5 V/s until all unstable atoms or clusters were removed and reproducible hydrogen adsorptiondesorption peaks were obtained. Phys.95 and -0. the electrode was rinsed thoroughly and transferred to the spectroelectrochemical cell for measurement.1 cm2 embedded in a Teflon sheath.e.8 V.72 and -0. It was found that.g. The same measurements were also performed at Pt surfaces in 0.. The oxidation of threonine and serine in the first potential cycle gives rise to a large current peak at around -0. The peak at -0. All experiments were performed at room temperature. J. (1) Effect of immersion potentials: The results show that the voltammetric features in the first potential cycle are strongly influenced by the immersion potentials. At immersion potentials more positive than -0. J.05 µm alumina powder to a mirror finish. more and more dissociative adsorbates were formed and accumulated on electrode surface. Finally. D. These results illustrated that the poisonous species can be formed spontaneously or in the potential region of hydrogen adsorption and that the kinetics of the formation of poisonous species depends on electrode potential applied. and then roughened in 0.0 V. three testing experiments were conducted. i. indicating that the dissociative adsorption can take place spontaneously. The Au electrode used for SERS measurement was roughened by a procedure similar to that reported by Weaver and co-workers. 16. the voltammogram reaches a steady profile shown in Figure 1c.2 V. The working electrode of Au or Pt was a rod with a geometric surface area of 0. and is indicated by the disappearance of the reduction current of oxygenated species in the reverse potential sweep. The excitation line was 632.64. ascribed to the adsorption of oxygen.2 V. ment with the model suggested by Horanyi et al. Cyclic voltammograms of Pt electrode in 0. serine [CH2(OH)CH(NH2)COOH]. (2) Effect of potential cycling in the hydrogen region: It was found that the hydrogen adsorption charge decreased with the increase of the number of potential cycling between -0.23 The Pt electrode was roughened with a method reported by Tian and co-workers.74.. Sweep rate: 50 mV/s. which were flame-annealed before immersion in electrolyte at a controlled potential. The reference electrode was a saturated calomel electrode (SCE). The larger oxidation current in both cases may be attributed to the bulk oxidation of their functional groups (CHOH). (3) Effect of adsorption in 0. 92. It is evident that some poisonous species are left at the surface and block all surface reactions involved in this potential region. As an example.. Weaver. The electrode was immersed in the solution at -0. These anodic currents decrease rapidly in the subsequent potential cycles between -0.0 V. approximately. The adsorption charge of hydrogen and the oxidation charge of glycine decrease with the increase of the immersion potential. 1988. A more detailed description of the spectroelectrochemical measurement was given elsewhere..4 V. The steady cyclic voltammetric profile of threonine and serine is similar to the one described in Figure 1c. and the electrode potential was scanned at first in the negative direction going to -0. 18.1 M NaOH solution containing 5 mM glycine. Results Cyclic Voltammetry of Amino Acids on Pt Electrode. Figure 1b shows the voltammograms of a Pt electrode in 0.30 V is ascribed to oxidation of adsorbed glycine.12 In the present work. Vol. The first two peaks correspond to hydrogen desorption with peak potentials slightly negative-shifted.58 V were observed and ascribed to the adsorption/desorption of hydrogen. M. The electrodes in cyclic voltammetric studies are Pt and Au beads. in both solutions for an adsorption at open circuit for about 3 min. and finally. It has confirmed also that the oxidation of the poisonous species occurs at potentials above 0. the Pt electrode was first mechanically polished with 0. Three anodic peaks appear at. The current that is increased above -0.

on one hand. Upon going positively at a scan rate of 50 mV/s. the large oxidation current observed in the presence of glycine can be attributed to the oxidation of glycine. Sci. Figure 5 illustrates the timedependent Raman spectra recorded on a roughened Pt electrode in glycine-containing solution together with the spectrum obtained in pure NaOH solution at -0.24 It is shown that both the hydrogen and the oxygen region are modified upon the introduction of amino acids. CO. Figure 4a). Then the band frequency and intensity gradually increased with time (spectrum b2 in Figure 5). X.1 M NaOH.1 M NaOH + 5 mM glycine (b) solutions. and oxygen adsorption is shifted to the positive potential direction with an additional oxidation current above 0.2 V. in each case. This may indicates that no characteristic reactions take place in this potential region. Q. After glycine was added. In the present case. G. which can be ascribed to the oxidation of the secondary alcohol in threonine to the corresponding carbonyl compounds. Einitial. It is important to note that. Figure 3 shows their steady profiles at Pt surfaces with the upper potential limit of 0. X. The Pt-H vibration yields a rather weak and broad band at around 2030 cm-1 in pure NaOH solution as shown in Figure 5a. Sweep rate: 100 mV/s. hydrogen adsorption current and amino acid oxidation current can be observed in these steady profiles. Tian. which is superimposed with oxidation of glycine and its intermediate oxidation products. This is indicated by a peak shoulder in the first sweep and the large decrease of the oxidation current in the second potential sweep. R. The electrode was immersed in the solution at -0. 1989.30 V. 18.. when the upper potential limit was increased to 0. and CN vibration mode. Can.3 V. 2002 Xiao et al.1 M NaOH + 20 mM threonine solution. which is different from that observed in Figure 1c. 100 mV/s.. (25) Ren. The first anodic current peak appears at 0.. Therefore. Sweep rate: 50 mV/s. the observed two oxidation peaks in Figure 4b can be ascribed respectively to the oxidation of glycine (the first peak) and the oxidation of Au surface. Figure 4b shows voltammograms of Au electrode in 0.7 V.1 M NaOH + 20 mM glycine. 16. the large oxidation current starts to appear at -0.25 The intensity of this peak did not change with time. D. Q. (24) Marangoni.1 M NaOH + 20 mM serine. In the first anodic potential sweep. S. the formation of adsorbed poisonous species occurred after the oxidation of glycine and oxidative desorption of them occurred at potentials above 0. hydrogen adsorption is partially inhibited. Cai. B. Vol. Figure 2. Cyclic Voltammetry of Glycine on an Au Electrode. Figure 4.1 M NaOH (a) and 0. no characteristic current can be observed up to 0. unless glycine was afterward added into the solution at the same potential. yielding poisonous species adsorbed at the surface. (c) 0. In the subsequent potential sweep. . Li. 67. the surface blockage was not as large and fast as that described above.12 V is consistent with that of reduction of oxygenated Au species.1 V. Surf.45 V. It is necessary to mention that potential cycling between -0. The results demonstrate that.e. the first peak could be decreased completely to the baseline in about eight cycles. No. The steady CV profiles could be reached in about three or four cycles. B. Figure 3b is in agreement with that reported by Marangoni et al. indicating that the surface was fully blocked.. Chem. Steady cyclic voltammetric profiles at Pt surfaces. a narrow and strong peak appeared at 2040 cm-1 (spectrum b1 in Figure 5).1 M NaOH + 20 mM threonine. 921. It is well-known that the Raman band located at the frequency region around 2100 cm-1 can only be assigned to Pt-H. Figure 3..60 V.0 V did not make much difference on the observed first voltammetric profile shown in Figure 4b. the first peak current decreases. This implies that the poisonous species would be partially oxidized at more positive potentials. Figure 2. (d) 0. S. Voltammograms of the first two anodic sweeps of threonine at Pt surface in 0. The second one appears at 0. 428.. Electrolyte: (a) 0.60 V.6 V and the polarization program started in the negative potential direction. while the second one increases.1 M NaOH + 5 mM glycine solution. (b) 0. G. If the upper potential limit was set at 0.8 and 0. and the total reduction of oxygenated species in the reverse potential sweep is nearly independent of the number of the potential cycling. Cyclic voltammograms of a poly-Au surface in 0. J. Smith. Further gradual decrease of the hydrogen adsorption and the threonine oxidation occurs in the subsequent potential sweeps.22 V. and on the other hand. the broad reduction peak at 0.90 V. 157-161. i. 1999. However.8 V. Z. In the reverse potential sweep. SERS on Pt Electrodes. -0. which is 200 mV more positive than that for oxidation of the Au surface when glycine is absent in the solution (cf. Xu. sweep rate.. This reaction may be immediately followed by further dissociation. Roscoe.6276 Langmuir. W.

Time interval: 100 s. E.2 V. X. amino acid oxidation. In situ SERS spectra of Pt electrode in 0. With the potential further going positively above 0. which is in an agreement with the results of cyclic voltammetry. Weaver. J.5 V. 323. 2002 6277 Figure 5. The onset potential for cyanide formation in serinecontaining solution was measured at -0. Y.2 V is due to either the further oxidation of cyanide to form solution (26) Ren. which is considered to be mainly due to the electrochemical Stark effect for adsorbed surface species. Xie. J. S. The band intensity seems to increase to its maximum when the potential was increased from -0. But here we mostly attribute such a decrease of intensity to the decrease of the coverage of cyanide.27.1 M NaOH solution and then increased by every 50 mV. Chen. However.2 V. which may be due to the increase of dipole-dipole coupling as the coverage of the cyanide increases.2 V. L. Chem. this band can be therefore attributed to the formation of cyanide on the Pt surface. Figure 8 shows the SERS on an Au electrode in the glycine-containing solution. 322. Chem.8 V. 1996. In situ SERS spectra of the Pt electrode in 0.8 to -0. especially at potentials around -0.at 2168 cm-1 has been detected. D. 1992.1 M NaOH + 5 mM glycine (b1. There is no characteristic Raman peak between 1600 and 2600 cm-1 at potentials below 0.70 V. .2 V. 561-566. SERS on Au Electrodes. No characteristic Raman band between 1600 and 2600 cm-1 can be observed at potentials below -0. Z. the immersion potential was set at -0. J. Another evidence is the increase in frequency with time. Interfacial Electrochem. 1984. probably only at potentials when oxidation processes take place.. such a process has already accompanied by a large oxidation current as observed in the cyclic voltammograms. Y. Tian. i. Therefore. A peak at 2120∼2135 cm-1 (29) Zou.e. Electroanal. because it is consistent with our previous Fourier transform infrared (FTIR) results of the formation of OCN. G.0 V. or the oxidation of the Pt surface. while the dissociation of other amino acids occurs at more positive potentials.90 V. indicating that the dissociation of threonine starts as soon as the oxidation process takes place. species. The band intensity increases much faster when the immersion potential is set positively. a maximum coverage of adsorbed cyanide has been achieved at -0. Lett. -0. B. The formation of cyanide starts at -0. The increase of the intensity shown in Figure 7 indicates a slow increase of the coverage of adsorbed cyanide in the potential region below -0.6 V. It is clear that dissociation of glycine takes place in a wide potential region including the hydrogen potential range. Li. No.1 M NaOH + 5 mM glycine solution at the indicated applied potentials. M.0 V. Figure 7. and then blocks the surface reactions as a poison.5 V in alkaline solutions. To clearly observe the dissociation process of threonine. 201-210. 100. Phys. Figure 6. A.6 V. which led to the deactivation of Pt surface to Raman sensitivity. Q.Adsorption of Amino Acids on Pt and Au Electrodes Langmuir. cyanate (OCN-) and carbonate (CO32-). The decrease in intensity in the potential region above 0.6 V. Phys. J. also at the potential when its bulk oxidation starts. and oxygen adsorption as well. in which a band assigned to OCN.1 M NaOH (a) and 0.6 V and keeps almost constant at potentials below 0.at potentials above 0. C. (27) Santos. Yao.70 V. Giordano. which is the onset potential of threonine oxidation. time interval. Vol. S.6 V. J.. M. while CO adsorption at the Pt surface is not stable when the potential is more positive than -0. Chem. 18. 16. respectively.26 because this band can be consistently observed at potentials up to 0. Einitial.8 V in 0. the band becomes broad and the intensity starts to decrease and then vanishes at 0. 319328.. In situ SERS spectra obtained on the Pt electrode at -0. It may be inferred that dissociation of the oxidation products is easier than that of threonine itself.29 Raman spectra obtained on the Pt electrode in threonine-containing solution are shown in Figure 7. further cyanide oxidation releases surface sites for hydrogen adsorption.26. 2000.. Z. Figure 6 shows further changes in the spectrum when the applied potential was increased positively...0 V. 100 s. 4237-4242. Cyanide formed as an intermediate is strongly adsorbed at Pt surface below 0. At potentials above 0.9 V when threonine was added into 0.13 The band frequency shifts from 2042 cm-1 at -0..2 V..28 The slow increase in the intensity indicates the dissociative adsorption of glycine is a slow surface process at -0.8 V to 2123 cm-1 at 0. Q. Electroanal. b2) solutions. Wu.. C.1 M NaOH + 20 mM threonine solution at the indicated applied potentials. Time interval: 100 s. Chem. (28) Sun.

According to the current results. Chem. the hydrogen adsorption is strongly inhibited. Y. Glycine is the simplest amino acid and the one adsorbed most strongly at the Pt surface. J.) Figure 8. It is reasonable in this model that the different configuration of the R-group would strongly influence the bond to the Pt surface. J. In contrast. The measurements performed in a serine. depending on both the immersion potentials and the adsorption time. it is shown in SERS that the dissociative adsorption of these amino acid molecules to cyanide is a rather slow surface process.. (See text for details. However.1 M NaOH + 5 mM glycine solution at the indicated applied potentials.g.14-17 In the strong alkaline solutions.. which leads to a weaker bond to the Pt surface.2 V. A. acetic acid solution. acetic acid ions). However. No. serine and threonine contain rather big functional groups. In situ SERS spectra of the Au electrode in 0. considering the amino acid molecule as a biligand.20-22 based on the FTIR measurement..and CO32-. The inhibition of hydrogen adsorption in the first potential cycle in the presence of amino acids is probably due to (1) the strongly adsorbed cyanide formed from the dissociation of amino acids and (2) the chemisorption of the amino acid molecules. the role of the amine group has been taken into account. an indication of no direct interaction between carbon and Pt atoms. the dissociation takes place more easily at a Pt than at an Au surface. A strong spectroscopic identification should be obtained at the (30) Zou. At potentials above 0. it might be evident that no distinct vibration band between 200 and 600 cm-1 was observed at -0. It is assumed that these amino acids are chemically adsorbed on the Pt surface by anchorage of the molecules to the surface by both the nitrogen and the adjacent carbon atom. which is an indication of a strong bond of the molecules to the surface. Chen. Z. In this model. This is evidence for a stronger interaction between amino acid molecules and a Pt surface.19 The above comparison indicates that the strong inhibition of hydrogen is mostly due to the presence of the neutral amine group in amino acid molecules in alkaline solutions. Figure 9. Obviously. model a is favorable in strong acidic solutions due to the positively charged amine group. Sadler. Strong chemisorption can then lead to the dissociation of these molecules. Parkinson.. the strong inhibition of the hydrogen adsorption therefore contributes to the chemisorption of amino acid molecules itself. Also. . 1999. Guo. while the dissociation of serine and threonine occurs along with the oxidation of their -CHOH group. This behavior is mainly a consequence of the neutral amine group involved in the adsorption configurations. At a Pt surface. We did not observe such a strong inhibition of hydrogen adsorption in acidic solutions. especially in the cases of threonine and serine. 16.30 Among these possible adsorption configurations. 20 s. it is problematic that this band is always overlapped with that of carbonate ions and aliphatic acid (e. time interval. where we can clearly observe two reversible hydrogen adsorption peaks with slight shifts of the peak potentials in the case of glycine. J. The amino acid molecule is adsorbed on the metal surface through both one of its carboxyl bonds and the amine group. in aliphatic carboxyl compounds containing alkaline solutions. From our results. This band is therefore ascribed to the interaction between Pt and the adsorbed cyanide. relying on the lowfrequency Pt-C. In their reports they described an IR shift around 1390 cm-1 as evidence for the original bonding between amino acid molecules and the Pt surface through a carboxyl group. Proposed adsorption models of amino acid molecule on metallic surface. and its intensity increased when potential was set at 0. Vol. Meanwhile. 1359-1360.6278 Langmuir. and it fits to the coordination chemistry. -0. Such a strong bond then leads to the dissociative adsorption. we might propose another adsorption model shown in Figure 9c. 2002 Xiao et al. such a bond would not strongly influence the hydrogen adsorption as described above. and on the other hand. Figure 9a is the adsorption model proposed for acidic solutions in the literature. Figure 9b is the one suggested by Horanyi and Rizmayer12 on the basis of the irreversible adsorption behavior observed by radiotrace measurements. and Pt-O vibrations. The crosses in the figure (×) indicate the bond broken in the dissociative reactions. which is accelerated by increasing the electrode potential or positive charge density of the surface. P.2 V for more than 20 s.. whereas a more positive potential is needed for the formation of a cyanide adlayer at an Au electrode.80 V.. appeared at potentials above 0.14-17 It was also suggested for alkaline solutions by Ogura et al. where a large amount of cyanide signal has been detected. J. the amino acid oxidation proceeds rather smoothly because the electrode surface is partially released by further oxidation of cyanide to solution species OCN.or threoninecontaining alkaline solution also show that the formation of cyanide occurs along with a large amount of oxidation current being observed. It was found that such a bond becomes weak at negative potentials and therefore only slightly influences the hydrogen adsorption. It is our intention to distinguish model b from c by SERS.8 V and even at potentials below -0.1 V. Commun. for example. Discussion The reactivity of the dissociation of amino acids to form cyanide is dependent on their molecular structures: glycine is more easily dissociated to form cyanide.18. Pt-N. such a strong inhibition is also not visible. Figure 9 shows the possible adsorption models of these simple amino acid molecules on metallic electrode surfaces.26 The band around 400 cm-1 could be observed only at more positive potentials.2 V. Einitial. adsorbed cyanide can be detected in a wide potential region including hydrogen adsorption region. which are formed in the dissociative oxidation at positive potentials. 18. this potential-dependent vibration can be also assigned to the adsorbed cyanide derived from the oxidation of glycine.

2002 6279 beginning of immersion and at negative potentials for the sake of the formation of cyanide in the dissociative adsorption. cyanide. Financial support from grants of Natural Science Foundation of China (NSFC) and Ministry of Education of China (MOEC) is gratefully acknowledged. the adsorption bond becomes stronger and leads to the dissociation of these adsorbed molecules. while that of serine and threonine molecules starts along with the oxidation of their CHOH hydroxyl groups. No. and then the dissociation takes place at potentials more positive than in the case of glycine. Acknowledgment. LA025817F . 16. and on the other hand. The hydrogen adsorption is strongly inhibited by the adsorption of amino acid molecules. Since serine and threonine have relatively larger space resistance than glycine due to the presence of an R-group instead of hydrogen. The possible position of the molecular breakage in the dissociative reactions is also shown in Figure 9. However. The dissociative adsorption leads to another adsorbed species. Vol. The dissociation of glycine starts in the hydrogen potential region. The formation of the dissociative products such as cyanide/ cyanate and carbonate implies the cleavage of the C-C bond but not the C-N bond. because on one hand. 18. the adsorption of them is weaker. The strong chemisorption model has been discussed by taking the role of the amine group into account. changing from 4-fold to 3-fold bonding decreases their space resistances. the bond from the molecule to the surface becomes stronger as the potential is increased positively.Adsorption of Amino Acids on Pt and Au Electrodes Langmuir. these molecules are getting easier to be dissociated due to the oxidation of their >CHOH group to a >CdO group. Summary The adsorption and oxidation of the amino acids were studied by cyclic voltammetry and surface-enhanced Raman spectroscopy. With the increase of the electrode potential.

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