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In situ FTIRS and EQCM studies of glycine adsorption and oxidation on Au(1 1 1) electrode in alkaline solutions
Chun-Hua Zhen, Shi-Gang Sun∗,1 , Chun-Jie Fan, Sheng-Pei Chen, Bing-Wei Mao, You-Jun Fan
Department of Chemistry, State Key Laboratory for Physical Chemistry of Solid Surfaces, Institute of Physical Chemistry, Xiamen University, Xiamen 361005, China Received 3 June 2003; received in revised form 9 September 2003; accepted 10 September 2003
Abstract Dissociative adsorption and oxidation of glycine on Au(1 1 1) single crystal electrodes in alkaline solutions were studied in the present paper using cyclic voltammetry (CV), in situ FTIR spectroscopy (FTIRS) and electrochemical quartz crystal microbalance (EQCM). In situ FTIRS results demonstrated that adsorbates derived from glycine dissociative adsorption are adsorbed cyanide anions (CNad − ). The CNad − species are stable on Au(1 1 1) surface in the potential region from −0.8 to 0.0 V, and can be oxidized when electrode potential is increased above 0.1 V. The oxidation of CNad − releases surface active sites for further glycine oxidation. The products of CNad − oxidation were determined by in situ FTIRS as cyanate (OCN− ), aurous cyanide (AuCN) and aurous di-cyanide (Au(CN)2 − ). The formation of Au(CN)2 − may initiate a dissolution of Au(1 1 1) surface atoms, which has been conﬁrmed by a loss of surface mass determined in EQCM studies. It has revealed also that at high electrode potential region glycine may be split on Au(1 1 1) surface to form AuCH2 NH2 and AuCOO− adsorbates. Further oxidation of these species yielded CO2 and –NH2 , and the AuCH2 NH2 may be also combined with surface Au oxide to form methylamine. The CO2 species produced in glycine oxidation are all retained in alkaline solutions to generate carbonate (CO3 2− ) and bicarbonate (HCO3 − ) species that were clearly determined by in situ FTIRS studies. © 2003 Elsevier Ltd. All rights reserved.
Keywords: Glycine; Adsorption; Oxidation; Au(1 1 1); In situ FTIRS; EQCM; Alkaline solutions
1. Introduction Glycine is the simplest structural block of protein and the smallest amino acid molecule. A better understanding of adsorption and oxidation properties of glycine on electrode surfaces is of signiﬁcant importance to elucidate the mechanism of complex metal-protein interaction, and to explore fundamental of interaction of different functional groups (–CHX , –OH, –NH2 , –COOH, etc.) with electrocatalyst surfaces as well. The adsorption and oxidation of glycine has attracted extensive attentions in recent years, including investigations of glycine on Pt single crystal electrodes [1–3], on polycrystalline Au electrode [4,5], and on nanostructured gold ﬁlm electrode . It is known that glycine molecule exists in neutral or acidic forms in gas phase, while in
Corresponding author. Fax: +86-592-2183047. E-mail address: firstname.lastname@example.org (S.-G. Sun). 1 ISE member.
aqueous solutions, the chemical conﬁguration of glycine varies from cationic (NH3 + CH2 COOH) through zwitterionic (NH3 + CH2 COO− ) to anionic (NH2 CH2 COO− ) form as solution acidity decreases . In our previous paper , adsorption and oxidation of glycine on nanoscale thin ﬁlm Au electrode in alkaline solutions were studied. We have revealed that glycine can be dissociated into cyanide (CN− ) adsorbate, and that in glycine oxidation, surface Au atoms can be dissolved through the formation of aurous di-cyanide (Au(CN)2 − ) species at high electrode potentials. Xiao et al.  have studied adsorption of simple amino acids on Pt and Au electrodes in alkaline solutions by using Raman spectroscopy, and three coordination models of amino acid molecules on Pt and Au surfaces were conﬁrmed in their studies, i.e. (1) through the terminal COO− group of fully unprotonated anions, (2) through both the nitrogen and the adjacent carbon atom of –CHR–NH2 group, and (3) through both the –NH2 and the –COO− on surface in considering the amino acid molecule as a
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super pure NaOH. The noise (RMS) of the measured frequency has been determined to be within 0. R R(ES ) − R(ER ) = (1) R R(ER ) where R(ER ) and R(ES ) are single-beam spectra collected respectively at reference potential ER and sample potential ES . The EQCM cell designed and used in this study is shown in Fig. 1500 interferograms of spectral resolution 8 cm−1 were scanned and co-added into each single-beam spectrum. It is obvious that the current peak observed in Fig. highly ordered (1 1 1)-orientation gold vacuum deposited on the quartz crystal. The apparatus employed in present studies was an EQCM model QCA917 (Seiko EG&G). a large and broad reduction current peak appears near 0. while the ES was shifted positively in a multi-step manner over the potential range from −0. m. 3. Up to now. In order to illustrate the surface structure effects.45 ng cm−2 Hz−1 ) for an AT-cut quartz crystal of 9 MHz . The aim of the present paper is to investigate further the electrochemical behaviors of interaction of glycine with Au(1 1 1) single crystal surface in alkaline solutions. EQCM is capable of detecting surface mass change in electrode|electrolyte interface at a nanogram range.1 M NaOH are shown in Fig. (d) solution bridge. i. 2a and b at 0.e. (b) C. in situ FTIR spectroscopy and electrochemical quartz crystal microbalance (EQCM) were employed in the studies. All solutions were prepared using Millipore water (18. S.-H. the SCE electrode was separated from electrochemical (IR) cell by a solution bridge made of a stopcock with two ends. The AuOH species has a brief lifetime and is converted ultimately to inert surface oxide. which occurs with a partial charge transfer .28 V. All IR results were presented as potential-difference spectra calculated using equation bellow. A saturated calomel electrode (SCE) was served as reference electrode. Solutions were deaerated by purging with pure N2 gas before experiment.g. All experiments were carried out at room temperature around 20 ◦ C. 2.6 to 0. has been calibrated to be 5. Different adsorption orientations of glycine vacuum deposited on Cu(1 1 0) surface were studied recently by Barlow and co-workers using reﬂection absorption infrared spectroscopy (RAIRS) and low energy electron diffraction (LEED) . m = −S f (2) speciﬁc adsorption of iodine . 10 mm in diameter. (EQCM–Au(1 1 1)). Zhen et al. (c) R. quenched with Millipore water. surface mass change per unit area. greatly enhanced the application of the EQCM [10.143 Hz. To minimize the loss of IR energy due to absorption of solution in the thin layer between Au(1 1 1) electrode and CaF2 IR window. is proportional to the change in resonant frequency. In the cathodic potential scan. The formation of oxide on Au(111) appears as a large and broad current peak around 0.11 V in the anodic potential scan is a character of OH− chemisorption on Au(1 1 1) surface to form AuOH. The Au single crystal electrodes were treated before each measurement using Clavilier’s methods .10 V. Fig.1250 C. The establishment of the ability to use a single crystal-grade working electrode. Sketch of EQCM cell (glass body and Teﬂon holder (shadow part)). they were annealed in a hydrogen–oxygen ﬂame. and glycine of analytical grade. (SCE).29 ng cm−2 Hz−1 through a method of . In order to avoid the interferences of ions. The Au(1 1 1) electrode employed in the in situ FTIRS studies is a disk of ca.) is denoted thereafter as EQCM–Au(1 1 1). e. Experimental Au(1 1 1) single crystal electrode applied in CV studies was prepared according to reference . The ER was maintained at −0. the highly ordered (1 1 1)-orientation Au electrode (Seiko Instruments Inc. Results and discussion Cyclic voltammograms of well-deﬁned Au(1 1 1) and EQCM–Au(1 1 1) in 0. It has tested that the drift of the measured frequency may be negligible in measurements under a cyclic voltammetric manner. the reaction mechanism of amino acid electrooxidation is still far to be well understood. i. This quantity is slightly smaller than the value expected from the Sauerbrey equation (5. 1. We can where the mass sensitivity of the crystal. (a) W.11]. Mllipore Ltd. such as K+ and Cl− from SCE electrode during the measurement.E.E. f. According to Sauerbrey equation . a CV of polycrystalline Au electrode is also displayed in the ﬁgure. Cyclic voltammetry (CV). 1. the electrode is pressed against the window so that the thickness of the thin layer is within a few m. which represents the reduction of surface oxide formed in the anodic scan.).8 V throughout the measurements.e. In situ FTIR experiments were carried out on a Nexus 870 apparatus (Nicolet) equipped with a MCT-A detector cooled by liquid nitrogen. (Pt-black foil). then transferred into electrochemical cell under protection of a droplet of Millipore water.0 M cm) provided from a Milli-Q Lab apparatus (Nippon.E.5 V. 2. / Electrochimica Acta 49 (2004) 1249–1255 bi-ligand.
It is worthwhile to note that the onset oxidation potential is close to the beginning of AuOH formation on Au(1 1 1) surface. The oxidation charge measured by integration of j–E cure between 0.0 V for 5 min. 2a). jPII . solid line). and occurs in two peaks at higher potential region.0 V for Fig. and that the jPI is increased sharply just after the current peak of AuOH formation on Au(1 1 1) surface (0.0 and 0. 5 min in order to accumulate glycine adsorbates on Au(1 1 1) surface.1 M NaOH solutions.1 M NaOH + 50 mM glycine solution recorded under different pretreatment conditions. 2a).5 A cm−2 . The decrease in reduction charge may indicate that the surface oxide formed in anodic potential scan is either consumed partially in glycine oxidation or dissolved into bulk solution due to interaction with glycine adsorbates when the solution contains glycine.8 and 0. Zhen et al. (– – –) CV of a polycrystalline Au electrode subjected to the pretreatment.0 and 0. and the charge of this peak is increased to 277.1 C cm−2 . The ﬁrst sharp current peak. and the oxidation current peaks jPI and jPII become both larger and reached to 306. 3 compares voltammograms of Au(1 1 1) electrode in 0. indicating that the oxidation of glycine in bulk solution was taken place in associating with the oxidation of glycine adsorbates accumulated on Au(1 1 1) surface during the pretreatment. 2a). while it is increased to 1771. Fig. Scan rate: 50 mV s−1 .0 V.6 V without pretreatment.6 V is 355. We can observe from this voltammogram that the oxidation current starts to appear at 0.8 and 0. A CV of polycrystalline Au electrode (dashed line) recorded under the same conditions is compared in the ﬁgure.0 V.1 M NaOH + 50 mM glycine solutions.17 V of intensity 269. Scan rate: 50 mV s−1 .1 M NaOH + 50 mM glycine solution at 0. In this case. (b) EQCM–Au(1 1 1) and (c) polycrystalline Au electrodes in 0.9 C cm−2 in the solutions free of glycine (Fig. respectively. 2. indicating the speciﬁc activity of Au(1 1 1) surface for glycine oxidation. The charge corresponding to the reduction peak in the cathodic potential scan is measured from the solid line to be 270. is at 0. no accumulation of glycine adsorbates occurred on Au(1 1 1) surface. This indicates that the chemisorbed OH− species on Au(1 1 1) surface may play a key role in promoting the oxidation of glycine . It is interesting to see that the jPI become almost a shoulder peak while the jPII remained in the voltammogram. This result signiﬁes that the oxidation of glycine adsorbates accumulated on Au(1 1 1) surface is a slow process.4 and 193.-H. jPI .5 C cm−2 . and the oxidation of glycine in bulk solution can be partially inhibited by the adsorbates. which is smaller than the value 285. is broad with its center near 0. indicating that the EQCM–Au(1 1 1) exhibits good quality of Au(1 1 1) surface structure. The voltammogram of the dotted line in Fig. Table 1 reports the effects of glycine concentration on its oxidation. (—) CV of Au(1 1 1) recorded after a pretreatment of potential cycling between −0. 3 was recorded as soon as that the Au(1 1 1) electrode after ﬂame treatment had been introduced into 0.9 C cm−2 acquired on Au(1 1 1) in the solution free of glycine (Fig.6 C cm−2 when the solution contains 50 mM glycine (Fig. The solid line represents a pretreatment of potential cycling between −0. 3. The jPI and jPII listed in Table 1 were acquired in the anodic potential scan on Au(1 1 1) electrode that has been subjected to a pretreatment of potential cycling between .39 V of intensity 184.5 V.5 A cm−2 . Cyclic voltammograms recorded in 0. 3. see Fig.9 A cm−2 followed by a shoulder peak near 0. (· · ·) CV of Au(1 1 1) recorded between 0. the second peak. 2b) are very similar to those of Au(1 1 1) electrode. Cyclic voltammograms of: (a) Au(1 1 1).11 V. / Electrochimica Acta 49 (2004) 1249–1255 1251 Fig. It is interesting to see that the amplitude of the reduction current peak in the voltammogram of dotted line is slightly increased. see that CV features of the EQCM–Au(1 1 1) (Fig.C. which may indicate a less dissolution of Au(1 1 1) surface oxide in the anodic potential scan for an Au(1 1 1) surface not covered initially with glycine adsorbates.
Before recording these spectra. / Electrochimica Acta 49 (2004) 1249–1255 Table 1 Comparison of peak current densities of glycine oxidation for different glycine concentration in 0.5 A cm−2 . implying that the jPII is correlated closely with solution species oxidation.0 V for 5 min to accumulate glycine adsorbates on Au(1 1 1) surface. and the bipolar band mentioned previously became a positive-going monopolar band. The ER was ﬁxed at −0. indicating the gradual depletion of OH− species in the thin layer associated to the dissociative adsorption of glycine.1 M NaOH solutions Cglycine (mM) jPI (A cm−2 ) jPII (A cm−2 ) 1 222. A series of spectra of glycine adsorption and oxidation on Au(1 1 1) electrode is displayed in Fig.6 V. The band near 2168 cm−1 can Fig. The broad positive-going band around 1650 cm−1 is as- AuNH2 CH2 COO− + Au → AuCH2 NH2 + AuCOO− (4) AuCH2 NH2 + 4OH− → AuCNad − + 4H2 O + 3e− (5) AuCOO− → Au + CO2 + e− (6) CO2 species will be converted into carbonate and bicarbonate in alkaline solutions. As illustrated by the insert to this ﬁgure. while the center of these bands is independent of ES .1 A cm−2 .1 V. Zhen et al.6 to 0. the positive peak and the negative peak of the bipolar band are respectively around 2109 and 2123 cm−1 when ES is at −0. 1402. which requires the participation of OH− species. CO2 + OH− → HCO3 − HCO3 − + OH− → CO3 2− + H2 O (7) (8) The consumption of OH− depicted by above equations will decrease pH value of solution according to the equilibrium. ES is indicated for each spectrum. the well-deﬁned Au(1 1 1) electrode was subjected to a pretreatment of potential cycling between −0. In situ FTIR spectra of Au(1 1 1) electrode in 0. 1583. The intensity of this band is increased continuously.5 V.8 and 0. the jPI is augmented slightly from 220. ER = −0. with the increase of ES . With the increase of glycine concentration from 1 to 50 mM in 0.1 to 269. It can be seen that.1 M NaOH solutions. NH2 CH2 COO− + Au → AuNH2 CH2 COO− (3) −0. appeared in the spectrum. 4 may be summarized below. 4.1252 C. The variation of IR features observed from spectra displayed in Fig.6 to 207. and then it was pressed on the IR window to form a thin layer for IR investigations. the main IR features in spectra are a bipolar band around 2115 cm−1 and a broad positive-going band near 1650 cm−1 . The intensity of these new bands is increased when ES is stepped to 0.6 10 263.-H. the negative peak of the bipolar band is shifted to higher wavenumber that conﬁrms the adsorption state of the CN− species.8 V while ES was varied from −0. six new negative-going bands.1 160. 1483.3 50 269.1 signed to H–O–H bending of water molecule .2 V. 4.8 and 0.0 V for 5 min.e. implying that they are all from IR absorption of solution species originated from oxidation of glycine adsorbates and glycine molecule in the thin layer between Au(1 1 1) and IR window.0 88. i.6 to 0. This bipolar band can be assigned to the difference in IR absorption of adsorbed cyanide species (CNad − ) at ER and ES [17–20]. H2 O = OH− + H+ (9) (2) When ES was increased to 0. locating respectively near 2168.0 V. while the jPII is increased markedly from 88. .1 M NaOH + 50 mM glycine solutions. 1382 and 1305 cm−1 .5 207.8 V. It is evident that CNad − is derived from dissociative adsorption of glycine on Au(1 1 1) surface. (1) When ES was varied from −0.
. Surface mass variations of EQCM–Au(1 1 1) electrode in (a) 0. The oxidation of CNad − at these electrode potentials may be described as below. which has a large stability constant of 2 × 1038 . .3 V. AuCH2 NH2 + 6OH − and Au(CN)2 − (2146 cm−1 ) are related to the CNad − species that generated from dissociative adsorption of glycine as represented by Eqs. The shift of the equilibrium from H2 O to H+ and OH− (Eq.4 and 0. These IR features may give indicative that at potentials above 0. Since Au(CN)2 − complex. which may be caused by three effects: (1) the direct oxidation of glycine in bulk solutions.18]. 5 Fig. . chains on Au(1 1 1) surface will not be determined by FTIR spectroscopy. the Au(CN)2 − species will diffuse away from Au(1 1 1) surface upon its formation. The band appeared around 2146 cm−1 can be assigned to IR absorption of aurous di-cyanide anions (Au(CN)2 − ) [20.3 V. 1402. Fig. AuCN (2230 cm−1 ) (4) As ES was increased further up to 0. and indicates the formation of aurous cyanide (AuCN) species from the oxidation of CNad − on Au(1 1 1) surface . (3) may be either oxidized into CO2 and –NH2 [17. The negative-going bands centered near 1402 and 1305 cm−1 can be respectively ascribed to IR absorption of CO3 2− and HCO3 − species . . AuCNad − + 2OH− → Au + OCN− + H2 O + 2e− (12) AuCNad − → AuCN + e− AuCN + AuCNad − → Au(CN)2 − + Au (13) (14) → Au + CO2 + –NH2 + 4H2 O + 6e− (10) or it may be combined with surface Au oxide to yield methylamine. (3) At ES = 0. As the –NH2 band near 1583 cm−1 is so strong that it distorted the H2 O deformation IR band at around 1650 cm−1 . The above IR results may imply that part of AuCN has been transformed to soluble Au(CN)2 − at 0. which is ultimately converted to HCO3 − and CO3 2− species in NaOH solution as described by Eqs.5 V. 1385.1 M NaOH + 50 mM glycine solutions. which come from the further oxidation of AuCN species at the same potential value of 0. / Electrochimica Acta 49 (2004) 1249–1255 1253 be assigned to IR absorption of solution cyanate species (OCN− ) . (2) the consumption of OH− in the thin layer.24]. The three IR bands of these species were continuously strengthened till ES = 0. It is worthwhile to note that the spectral baseline has been distorted obviously above 0. is extremely stable. 1382.26]. and then their intensity was maintained almost constant at 0. –Au–CN–Au–CN.5 V. chains [25. The dissolution of Au in glycine oxidation at higher potentials can be also conﬁrmed by EQCM studies. the quantity of AuCN is certainly small that is conﬁrmed from the small intensity of the band.3 V. (3)–(5).4 V. 1483. . two new negative-going bands centered near 2230 and 2146 cm−1 appeared. The species of OCN− (2168 cm−1 ). 5.C. which signiﬁed the gradual accumulation of glycine oxidation products in the thin layer. If the polymerization takes place on Au(1 1 1) surface. and the surface AuCN species yielded the band near 2230 cm−1 in spectra. AuCH2 NH2 + AuOH → Au + AuO + CH3 NH2 (11) The IR absorption due to scissors deformation of both –NH2 species and NH2 group in methylamine may contribute to strengthen the band near 1583 cm−1 . . the intensity of IR bands near 1583.3 V. It can be seen that the bands near 1402 and 1382 cm−1 were merged to form a broad band centered at about 1385 cm−1 . (3) the partial overlapping of the –NH2 scissors deformation band with the H2 O band. It is known that the AuCN species may produce inﬁnite parallel linear .-H. and 1305 cm−1 were augmented dramatically and simultaneously. Zhen et al. . which led to the decrease of H2 O in the thin layer. the electrode will become inert and the . 1402. and the bands near 1483 and 1382 cm−1 may be ascribed to asymmetrical deformation and symmetrical deformation of –CH3 group . (9)) became predominant owing to the consumption of OH− . The negative-going band around 2230 cm−1 corresponds to IR absorption of adsorbed C≡N species. has been generated in glycine oxidation.1 V the AuCH2 NH2 formed through Eq. and 1305 cm−1 is strengthened again in the spectrum. 1483. And the intensity of the bands around 1583. (4) and (5). –Au–CN–Au–CN. Scan rate: 50 mV s−1 . . signifying that CO2 species. The band at around 1583 cm−1 may be assigned to the scissors deformation of –NH2 group in alkaline medium .1 M NaOH and (b) 0. . As the further oxidation of AuCN to form Au(CN)2 − is taken place at the same potential.
A. Perez. M. 5a. C.  H. –NH2 . the loss of surface mass (− m) is negligible (5. 482 (2000) 32. Lee. Surf. Chen.P.Y. M. Uhm. Lei. the CO2 generated in glycine oxidation is retained as CO3 2− and HCO3 − species in solution of the thin layer between Au(1 1 1) electrode and CaF2 IR window. E. The present studies have provided a comprehensive description at molecule level on the dissociative adsorption and oxidation of glycine on Au(1 1 1) electrode in alkaline solutions. Niu. Li. Sci. M.  X. S. Chem. Chen. References  F. The . In alkaline solutions. Chem.1 M NaOH solutions containing different glycine concentration. 413 (1996) 131. 155 (1959) 206. Electrochem. Commun. Electroanal. Aldaz. Dong.A.H.  K. M. J.G. Gu. Vazquez. Colloids Surf.2 87. However.C. 1382. C. Chim. As can be seen in curves of Fig.G.3 ng cm−2 that is 7. Z. when Eu was scanned up to 0. Adzic. Yao. J. 2 (2000) 646. When electrode potential is higher than 0. Consequently.G.  H.  H. S.8 V. Morallon. J. Nakayama.  F. Phys. Vazquez. 401 (1998) 322. Uosaki.  S. Morallon. Hanawa.W. Morallon. T.3 ng cm−2 has been determined in a 0.L. A. Chem. illustrating that high concentration of glycine may lead to increase the loss of surface mass of Au(1 1 1) electrode. Phys. Tian.G. Table 2 lists the loss of surface mass of EQCM–Au(1 1 1) electrode in a complete cycle of potential scan from −0. K.-H. Richardson.8 V Cglycine (mM) 1 10 50 − m (ng cm−2 ) 62.L. / Electrochimica Acta 49 (2004) 1249–1255 Table 2 Variation of surface mass change of EQCM–Au(1 1 1) electrode for different glycine concentration in 0. F. Huerta.3 V. Electroanal. Education Ministry of China (01101) and National Key Basic Research and Development Program (2002CB211804).1 M NaOH solutions without and with 50 mM glycine.L.1 M NaOH solutions in a complete potential scan from −0. Chem. B 103 (1999) 682.8 to 0. J. Chem.W. M.  J.J.  F. Vazquez. Nakayama. Wu. Xiao. A. E. J. Huerta. J. Uchida. Chem. Electroanal. S. A. Huerta. Perez.R. Such dissolution has been conﬁrmed quantitatively by EQCM studies. 1402. S. Gu.S. M. J.J. J. Ye. the pH value of solution in the thin layer is decreased gradually along with glycine oxidation.3 compares surface mass change per unit area ( m) of EQCM–Au(1 1 1) electrode in 0. i.L. Fan.M. Electroanal. 43 (2001) 2111. J. Armand. Seki. J. Kobayashi.J. Acknowledgements This work was supported by grants from National Natural Science Foundation of China (90206039.8 to 0. L. H. Sauerbrey. J. Quijada. 449 (1998) 101. CH3 NH2 . 1483. Nishihata.  S. in which a loss of surface mass of 92.  N. J. The dissociative adsorption of glycine on Au(1 1 1) surface leads to produce strongly adsorbed CNad − species that gives rise to IR absorption near 2115 cm−1 . Golden. Y. Y. Watanabe. Miho. the CNad − can be oxidized successively to OCN− (2168 cm−1 ).Y.e. Commun. and CH3 NH2 . Corros. the main conclusions may be drawn as the following. The data illustrated that − m is augmented with the increase of glycine concentration.  K. 489 (2000) 92. Sin. Petit. S.A. H. Y. J. 2 (2000) 48.R.  J. –NH2 . Electroanal. when the upper potential limit (Eu ) was lower than 0. Ogura. Lipkowski. Clavilier. Sun.8 V in 0. Tak. AuCN (2230 cm−1 ) and Au(CN)2 − (2146 cm−1 ). 205 (1986) 267. The oxidation of glycine at electrode potentials above 0. Tian.6 V and back to −0. Huang. J.  A. Varela. Through studies of cyclic voltammetry. Chen. D.4 ng cm−2 ) in a complete cycle of potential scan. Q. Electroanal. J.  F.1 M NaOH solution containing 50 mM glycine and in a complete potential scan from −0. R.B. dernier species may be derived from a surface combination of AuCH2 NH2 adsorbate with surface Au oxide (AuOH). Sun. Quijada. Chem. Acta Phys. and have thrown a light on elucidating the interaction mechanism of amino acid molecule with Au single crystal surfaces. Barlow. Electroanal.M. 467 (1999) 105. Electroanal. Conclusions The goal of the present paper is to investigate the dissociative adsorption and oxidation mechanism of glycine on Au(1 1 1) surface in alkaline solutions.H. Kitching. L.  C. A 154 (1999) 201. 19 (2003) 60. and 1305 cm−1 appearing in the in situ FTIR spectra. Huerta.G. It has revealed that the formation of Au(CN)2 − species led to the dissolution of Au atoms from Au(1 1 1) surface. C. Rodes. Berlouis. Morallon. Chem. K. Aldaz. J. The glycine oxidation products at high electrode potentials. Philpott. Chem. Zhen. J. N. Aldaz. Gordon II.  S.8 ng cm−2 measured from curve b recorded in glycine-free NaOH solutions. the formation and dissolution of Au(CN)2 − species were determined and attributed to the main reason that induced the dramatic loss of surface mass of Au(1 1 1) electrode in a potential scan up to 0. J. Haq.6 V.1 V may produce CO2 . As a consequence. Nakaoka. S. Electroanal. E.1 V.1254 C. 20373059). Sci. 4.C. J. A. Chem. in situ FTIR spectroscopy and electrochemical quartz crystal microbalance.M. Zhen et al. − m has reached 92.L. Y. Electrochem. CO3 2− and HCO3 − were evidenced by IR bands at around 1583.8 to 0.6 V where Au(CN)2 − species generated. Z. Lori. Langmuir 4 (1988) 337. E. 421 (1997) 179. J.6 92.G. K. 340 (1992) 213.V. T.6 V then back to −0.E. J. Chem.J. S.6 and back to −0.Q. Strbac. Naohara.2 times larger than the value 12.  K. Ogura. J. Langumir 18 (2002) 17. Kunimatsu. Sun. W. Sun.  G. Vazquez. 403 (1996) 169. 445 (1998) 155. Electroanal. Z. S. Cases.
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