ecvochemstry Communications 4 (2014) 31-33 Contents ists available at ScioneoDirect Electrochemistry Communications ELSEVIER journal homepage: www.elsevier.com/locate/elecom Short communication Decoupling surface reconstruction and perchlorate adsorption on Au(111) UE. Zhumaev* LV. Pobelov*", AV. Rudnev *" A. Kuzume™', Th. Wandlowski*! + beprment fami an Bochemsry. Unversity fem Fesrase 3,012 fem Stand ANU Frumkin sito ys CRemizy ond crochet, Rian Acer of scence, Meow 1998, usa ARTICLE INFO ABSTRACT ‘rl sy Received 1 Api 2014 Receive neve fem 1 Ape 2014 ‘cepted 16 Aoi 2014 ‘alte onine 24 Apr 2014 ewer att) Perera asoeion Sie eonsraton 1. Introduction ‘Adsorption and desorption of supporting electrolyte ions are involved in various important electrochemical processes on noble metal electrodes, such as hydrogen adsorption, surface reconstruction, underpotental ‘deposition surface oxidation and oxygen evolution [12] In general, the anions of common supporting electrolytes adsorb stronger than cations land have a greater influence on electrochemical processes. On gold sur- Faces, C10, s the weakest adsorbate [3), but the studies on its adsorption Aare scarce and the conclusions ae rather controversial [4-6]. ‘Adsorption and desorption of CIO, are fast processes on polyerystal- line Au electrodes 7,8) and therefore are characterized by symmetric ‘cic voltammograms (CVs) at low scan rates [9,10], The symmetry is ‘not the case for CVs of Au(111) electrodes in C10, -containing solutions even at 10 mV's_* [4] (Fig. 1, dotted). The reason for the asymmetry could be 1) the surface reconstruction of a Au(111) electrode; 2) a rearrangement within the adsorbed COs. layer; or 3) some other intrinsic properties of the Au(111)/ClO, interface, eg. slow charge ‘ansport [411-13], Although some authors [8,12,14] speculated that ‘the potental-induced surface reconstruction, Au(111) ~ (p x V3) ~~ ‘Au(111) — (1 x 1) might cause the asymmetry of CVs, it was not proven yet. Respectively, no methods were reported to decouple the “pure” adsorption desorption of anions. 7 Coespnding author Tel +4 31 6314254; fe: $4 316313964 ‘Ema adie ahunaevBac wae (UE Zune) URL pwn (UE. Zama) nop doorg 10. 1019}eecom20140409 138-2481 2014 seer BA igh resone. (On Au(111)etecrodes, the investigation of CO, adsorption is hampered by a simultaneous surface reconstruc tion, We demonstrate that these two proceses can be decoupled in yc voltammograms bya proper choice of ‘the scan ate and of then potential. Our approach allowedthe establishment ofa elation Detween potentials of zero charge forthe reconstrcted and unrecontructed Au(T11) surfaces. (© 2014 Elsevier BN. Allright reserved In this work, we present the voltammettic and spectroscopic in- vestigation of the adsorption behavior of C10, on Au(111). We dem- onstrate that the slow surface reconstruction is the only process responsible for the asymmetry of CVs and propose an experimental protocol to prevent it. Based on our experiments, we obtain the relation between the potentials of zero charge for reconstructed and unrecon- structed Au(111) surfaces, 2 Experimental Allsolutions were prepared using Milli-Q water (18 Mf, 3 ppb TOC), and 70% HO, (Suprapur, Merck). and purged by argon (5 N,Carbagas) prior to and during each experiment. All measurements were carried ‘ut at room temperature (25 + 1 °C). Glassware and Teflon parts were cleaned by boiling in hot 40% HINO: followed by several cycles of boiling and rinsing using Mili-. water. Cyetic voltammograms were measured in a two-compartment glass cell using an Autolab PGSTAT3O2N. A half-bead Au(111) electrode (A = 0023 cm?) was used as a working electrode. A hydrogen-loaded Pd wire and a Pt mesh served as the quasi-reference and the counter electrodes respectively. To minimize the solution resistance without disturbance of the current distribution, the reference electrode was placed ~1.5 em fat from the working electrode. The remaining solution resistance was partially compensated to achieve the residual resistance of 9-10 0. The latter was important fora good signal-to-noise ratio Before each experiment, the Au(111 electrode was annealed in butane fame and cooled in Ar atmosphere. Contact with the solution was2 Ur 2aumae etal / Becchemiy Communications 44 (2014) 31-33, Integrated intensityla.u, Oa oo os Evs (MSE) Fig 1.curves: Cs (cal the eft ofA 111 fn. CIO fs (dashed and second (done) ges of hermally-reonsrucea sac (10m *) ana espns ofthe une onsucted suc (sl) ecorded staring Fom 03 (18 ") mba: normale’ negated itenstes of (ale on the ght) baie by SERA spectroscopy ding th potive (mal neste) pte sans The ference spectrum sce t= V. Above Ell tee Cvs eae ‘made under potential control (at — 0.55 V) in the hanging meniscus configuration All CVs are presented as Cvs E plots, where C (=v) is a pseudocapacitance, j — a current density, and v — a potential scan rate. Al potentials in the present work are quoted with respect to MSE (Hgitig:$04,K,80; at) ‘Surface-enhanced infrared absorption (SEIRA) spectra were mea- sured using a lab-made Teflon cel. A 20 nm-thick quast-Au(111) fi electrode evaporated on a Si prism was used as the working electrode [15]. hydrogen-loaded Pd wire and a Au wire served asthe reference and the counter electrodes. For each spectrum. 16 interferograms with the esolution of cm ' were acquired and averaged during a potential sweep with the rate of 10 mV #.The acquisition time was about 54s per spectrum, and thus each spectrum represented the average IR response of 4 mV-wide potential intervals. 3. Results Fig. 1 shows the fist wo consecutive potential cycles ofa freshly, ame-annealed Au(111) electrode, recorded at 10 mVs in 0.1 M HCIO, in the “double-layer” region (dashed and dotted curves) after contacting electrolyte at 0.5 V. All subsequent CVs were identical to the second (steady-state) cycle (Fig 1. dotted). The first cyte differs from the second due tothe lifting ofthe thermally-induced reconstruc- tion Au(111) ~ (22. 93) [12.16], The anodic and cathodic peaks in the steady-state CV are assigned to ClO, adsorption and desorption respectively [4-6,17]. Our SEIRAS data also support this assignment: ‘upon development ofthe anodic and cathodic peaks, the integrated band intensity of veo gradually increased and decreased (Fig. 1 symbols). The steady-state CV was asymmetric: C103 adsorption and desomp- tion peaks were separated by ~0.12 V (Fig. 1, dotted), in agreement with literature [4,5,12,13,16}.To define processes responsible for this asymmetry, we recorded the series of CVs starting from the upper ver- tex potential E, = 03 V to dflerent lower vertex E, potentials (Fig 2). ‘We note that at 03 V the Au( 111) surface is unreconstructed | 18-20), ‘The CVs obtained were symmetric for > —0.15 V. Further decrease (of E led tothe shift ofthe adsorption peak to higher potentials, while the desorption peak remained unchanged. ‘We explored the effect of scan rate v on the CVs recorded starting from £, = 03 V to = —0.65 V. Positions ofthe peak maxima, extract- cd by fitting with Gram-Charlir function, vs Ig(v) are presented in Fig 3. Against the expectations, the peak-to-peak separation decreases withthe increase of v and reaches a constant value of -20 mV at v 10-1005", as exemplified by the CV recorded at 18 Vs "in Fig. 1 solid), 100. “04 015 00 4 Evs (MSEWV Fig 2 Series of sof Au 11) 4901 MHCIO (10 V5) eared staring ram upper ‘eres ptenal 03 V to dierent ower verte potenti. 4. Discussion 4.1. The origin ofthe asymmetry in cyclic voltammograms Inthe steady-state CV (Fig. 1, dotted). the adsorption currentof CIOs first gradually increases and after a certain (critical) coverage of C10, is reached suddenly drops, causing the asymmetry ofthe adsorption peak. Hence the resulting peak might consist not only of C105, adsorp- tion but also of rearrangement within the adsorbed C10, layer [4]. If this the case, CVs recorded at coverage values higher than the critical should also be asymmetric. However, such CVs are symmetric (Fig.2) ‘and suggest the absence ofthe interlayer rearrangement during CIO, adsorption on Au(111). These symmetric Cs also suggest the absence ‘of the diffusion and charge transport limitations upon adsorption/ desorption of C105 “The process causing the asymmetry starts at ~0.15 V, and itis ‘enhanced at lower potentials (Fig. 2). Identical behavior was observed for the potential-induced surface reconstruction process, Au(111) — (1x1) > Au(111) — (p % ¥3) [16,18,19]. Therefore, we conchide that Au(111) surface reconstruction in HCIO, solutions isthe only pro- ‘ess responsible for the asymmetry of the CVs in the double-layer region. Inn attempt to separate relatively fast 10g adsorption from the slow potential-induced surface reconstruction, we measured Cs with different scan rates v (Fig. 1 solid) We found thatthe reconstruction, ‘canbe prevented by usingv> 10Vs_ (Fig. 3). However, tis important that the starting potential is higher than —0.15V, ie. in the stability range of the unreconstructed Au(111) surface (Fig. 2). A similar oo] 4, 20st) 0 2 oes aviv 8") Fie 2Fostion ofl; adsorption (a) and desorption (*)peaksn CVs oF A111) in ‘OF MIO, measired wh ier snes sorting rom the pe vertex poeta (03 Vtothe lower etex potential ~ 0.5 ¥, a exemplified by sol Ene nF The rumbesindeate the crespending slope and ht tandard deviations (in brackets). ‘Tecra nde the poe cotton fetes don essed SE. aeeUE Zhuo eal) ecrochersty Communications 4 (2014) 31-32 2 ‘ 5 Q2 = &, Sa) é : i | ‘Evs (MSE) ig 4 Caclated charge ference betoen (22% ¥3) and (1 1) structs ofthe ‘Avi surface a poten. The aumbcriniates the corresponding slope ands Standard deviation (n rakes) Eissame as nF ‘technique was used to separate the fast adsorption and relatively slow oxidation processes of HCOOH on Pt(111) [21]. Atv = 10 Vs", the potential range ofthe potential-induced surlace reconstruction (=0.15 V-—0.65 V) is scanned in 0.1 s. This value indicates atime scale fr the initiation ofthe potentia-induced surface reconstruction, Au(LI1) = (11) > Au(t11) = (px ¥3). 42, Potentials of zero charge ‘The CV measured at 18 V s-* (Fig. 1, solid) represents the pure response of the Au(111) — (1x 1) surface (Fig. 3). In this CV, the peak-to-peak separation is -20 mY, which suggests that the adsosption/desorption of CO, onyfrom the Au(11T) ~ (1 1) surface js quasi-reversibe [9,10]. This CV coincides with the CV containing the contribution from Au(111) — (22 x »/3) surface (Fig. 1, dashed) at potentials above Fo (Fig. 1), where STM results showed the existence ‘ofonly the (1 1) structure 18,20}. Therefore we assume that interfa- Cal state above Eis the same for both these CVs. The late allows us to caleulate the charge difference between the electrochemical interfaces ofthe Au(111) ~ (22 « V3) and Au(111) ~ (1 1), ata given potential X,as follows: 491) wire G(E) and Cy) are pseudocapacitance values from dashed and Solid CVS of Fig. 1 respectively. We note that + Aq(X) and —Aq(X) refer to the liquid and solid parts ofthe interfaces respectively. By changing X, we obtain the dependence of aq on potential (Fi. 4). Values of aq(F) in Fig. 4 correspond to the charge difference between the interfaces ony at potentials where the (22 413) structure isstabl, ie below the onset ofthe ling of the reconstruction, -0.05 V [12] AL both interfaces, no chemisorption occurs below —04V (Fig. 1, dashed and slid), soin this range, the charge inthe solution par ofthe inter- {ace is determined in fist approximation as 4B) ~G(p26-E), 2 were Cis a capacitance, andi represents either (1 1) structure oF (22% V3): =e ‘Therefore, at = —04 V: Aq(E) (E)-AaE) = Bae, CDC Cur (Ca) E: @ Linear fitting of Aq(E) at E = 0.4 V gives the potential at which es 4q 0.78 (Fig. 4), Hence from Eq, (3) at E= E follows: = Cue) Cu BE + Cue B®, ® Poy, 851. pec,-0.116, 6) Cup ~ G) = 3:13 nF em”? (the slope ofthe fitted line in Fig 4), and Cy = 21 nF cm? (the half height ofthe sotd CV in Fig. 1 at —0165 V). We note that use of Eq, (5) requires potential values vs. MSE, Eq. (5) is the relation between the real pzc values, due to the assumption in Eq, (2) but nevertheless canbe used as an approximation when the pzc values are affected by the anion chemisorption. Eq (7) was checked using the pzc, = —0.08 V measured in 0.01 M HCIO, [12], where we assume the negligible effect of the chemisorption Calculated pzey- = ~0.18V isin good agreement with an experimental value of ~0.17 V [12]. For 0.1 M HCIOs, the only available experimental value ofpze,= —0.11 + 0.04 V [22] was used to calculate eye = —021 + 003 V. 5. Conclusions Surface reconstruction masks equilibrium processes on Au(111), electrode in the double-layer region, and hence makes the interpreta- tion ofthese processes difficult. The fast anion adsorption and desorp- tion processes can be decoupled from the slow surface reconstruction by measuring cyclic voltammetry at proper scan rates and initial potentials. Conftict of interest The authors declare no conflict of interest. Acknowledgements ‘This work was supported by SNF (200020_144471), CTI (13696.1), and the University of Bern AK. acknowledges a Marie Curie fellowship (FICAMD. AR. acknowledges FP7 project ACMOL (618082). References 11] A.Wiecows Inertial elecrchemisry. Theory, Experiment na Appears Masel Der Ines NewYork 1998 12] BX epi Smee i Stine NM Mat Fay [3] AtamelnjHeeooal hem nef coche. 138 (1982) 95 [a] angerste-Kenowsta BE: Conway. A Hamlin, Stocovcu, Becrochim Acta 51088) 1051 15] Angerstein-Kovlowska, BE, Conway. A. Hamelin. Stiovic, J Eetoon (hem nerf lecaem, 28 (1987 29 16) RE Conny Pro Sr 8 #9 (1985) 33. [PH Angesten esis, RE. Conway, 8. art} Mona, Hecrounal Chem. toe lectracem, 100 (1979) [s) Amel AN Mars fecal Chem. 407 (1906) 13. Is] 5 Sevan, leaders. Aca 11 (1968) 31, Ho] Arges Kelowsk, Kings BE. Conway | etroanal Chem etal kuch 75 (1977) 45. un) easy Wandisle DAC Keb. Eecroa cha. 414 (1855) 200 2] DAL Kal} Scbaeer,Eletocu. 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