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Electrochemical reduction of graphene oxide and its in situ spectroelectrochemical characterization

m*a Antti Viinikanoja,*a Zhijuan Wang,b Jussi Kauppilaac and Carita Kvarnstro
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Received 3rd July 2012, Accepted 20th August 2012 DOI: 10.1039/c2cp42253k The electrochemical properties of self-assembled lms of graphene oxide (GO) on mercaptoethylamine (MEA) modied rough Au-surfaces were studied. The lm deposition process on MEA primed gold was followed by surface plasmon resonance measurements and the lm morphology on 3-aminopropyltriethoxysilane primed Si(100)-surface was studied by atomic force microscopy. The deposited few layer thick GO lms on gold were electrochemically reduced by cyclic voltammetry simultaneously as the structural changes in the lm were recorded by in situ vibrational spectroscopies. In situ surface enhanced infrared spectroscopy results indicate that the eect of the applied potential on the GO structure could be divided into two parts where the changes occurring at moderate negative potentials are mainly related to changes in the double layer at the lmelectrolyte interface and to hydrogen bonding of intercalated water between the GO sheets. At potentials more negative than 0.8 V vs. Ag/AgCl the reduction of GO starts to take place with concomitant conversion of the dierent functional groups of the lm.

Introduction
A pristine graphene sheet possesses high electron conductivity1 and fast heterogeneous electron transfer rate at the graphene sheet edges,2 properties that are crucial for application in electrochemical devices in energy storage or production or in electrochemical sensors of dierent kinds.35 Since the revival of the investigation of graphene in 20046 chemical exfoliation of bulk graphite by strong oxidants or strong acid intercalation has been developed with the expectation of obtaining graphene like materials on a large scale and at low cost.3,4 The harsh treatment of graphite in the production of bulk graphite or graphene oxide (GO) excludes or depresses the properties found in pristine graphene sheets. As a result, the graphite oxide or GO is a highly hygroscopic, electrically insulating material, and its stoichiometry is shown to depend on the method of preparation and on the kind of graphite used.7 Subsequently, the chemically oxidized graphite must be reduced by chemical, thermal, or electrochemical means to retain at least some of the graphene structure.8,9
a

Turku University Centre of Materials and Surfaces (MatSurf), Laboratory of Materials Chemistry and Chemical Analysis, University of Turku, Vatselankatu 2, 20014 Turku, Finland. E-mail: antti.viinikanoja@utu., carkva@utu.; Fax: +358-2-333 6700; Tel: +358-2-333 6714, +358-2-333 6729 b School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore c The Finnish National Graduate School in Nanoscience (NGS-NANO), Nanoscience Center, P. O. Box 35, 40014, University of Jyva skyla , Finland

The electrochemical reduction was introduced as a fast and clean way (i.e. no contamination from reducing agents) for producing a partly recovered sp2 lattice.10 Especially in manufacturing exible reduced graphene oxide (rGO) lms with complex patterns of a specic thickness electrochemical reduction has shown its potential.11 Graphite or GO can be electrodeposited and simultaneously reduced as thin conducting lms from buered aqueous solutions in a wide pH range12,13 or from ionic liquids.14 The ionic surface groups on the GO sheets enable a thin lm preparation by the electrostatic layer-by-layer self-assembly technique.15 The method of fabrication and the way of reduction of the GO lm inuence the nal rGO product and its electrochemistry. In comparison to thermally reduced graphene oxide that contains a large amount of structural defects the chemically or electrochemically reduced GO contains a higher amount of oxygen containing groups.16 Electrochemical reduction has been reported to only partially remove the oxygen containing functionalities leaving groups mainly in the basal plane due to a faster electron transfer rate around the edges of the GO sheets.17 While electrochemistry alone cannot give details about structural changes in thin lms it is often applied in combination with a spectroscopic technique.18,19 We have previously used surface sensitive IR techniques to follow the formation of self-assembled mono- and multilayers to probe the structure, organization, chemical composition, and interactions within these thin lms.20,21 Previously, the thermal reduction of single and multilayer GO was studied by these IR techniques after the reduction process and the eect of intercalated water between the GO sheets on the nal reduced
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structure was discussed. The intercalated water was found to aect the defect formation and carbonyl formation in multilayered graphene oxide lms.22,23 By combining infrared absorption spectroscopy and electrochemistry, the evolution of oxygen containing defects can be followed in situ during the electrochemical reduction of GO. In this work in situ Surface Enhanced Infrared Spectroscopy (SEIRAS)24 was used with quasi-single crystalline metal lms deposited on high refractive materials in attenuated total reection (ATR) geometry together with cyclic voltammetry. SEIRAS enhances the signal-to-noise sensitivity by a factor of 1050 higher than that of IR reection absorption spectroscopy which makes it a superior technique in studying reaction processes on surfaces. We focus on the electrochemical reduction in the aqueous media of a few layers of GO deposited by self-assembly on the roughened gold plated reection element. Using the ATR geometry i.e. entering the lm from the backside through the substrate we can minimize the interference from electrolyte contribution to the spectra and get the main signal from intercalated water and the potential dependent change in functional groups in the GO. In situ surface enhanced Raman spectroscopy (SERS) and atomic force microscopy (AFM) were further applied for rGO characterization.

30% H2O2 was added to the mixture resulting in a bright yellow coloured solution. The resulting mixture was washed with HCl and distilled water after which graphite oxide was obtained. The obtained graphite oxide was dispersed in water at a certain concentration and subsequently sonicated to obtain GO. UV/Vis (GO): 231(pp*), B300 nm (np*); rGO, reduced with hydrazine: 270 (pp*), >300 nm (increase in absorbance).26,27 IR (graphite oxide): 3615 (sh, COH), 3410 (COH), 3210 (H2O), 1740 (CQO), 1620 (CQC, H2O), 1049 (CO), 14001300 (OH, COH), 12001000 (ArOH), 986 (sh, COC), 848 (COOC) cm1.28 Preparation of the substrates An Au-minielectrode (CHI101, 2 mm dia., CH Instruments, Inc.) was mechanically polished with an EtOH wetted polishing cloth (Struers, DP-Nap) using diamond paste of gradually ner grades (Struers, 3, 1, and 0.25 mm) with careful wash by EtOH in between. The mechanically polished electrodes were electrochemically cleaned in 0.5 M H2SO4 (Aldrich, Suprapur) using cyclic voltammetry recording 50 potential cycles between 0.0 and 1.2 V at 100 mV s1 vs. a Hg/HgSO4 reference electrode. In SERS measurements, the Au-minielectrode was additionally roughened electrochemically in 0.1 M KCl before the electrochemical cleaning step based on the previously reported procedure.29 Microscope glass slides and Si(100) wafers (Okmetic, Finland) for polarization modulation infrared reection-absorption spectroscopy (PM-IRRAS) and AFM measurements, respectively, were cleaned in fresh piranha solution (concentrated H2SO4/30% H2O2 (3 : 1)), rinsed thoroughly with Millipore water and dried. A gold lm (ca. 100 nm) was evaporated on microscope slides using the Edwards E306A coating system. The microscope slides were previously covered by an evaporated chromium layer (ca. 5 nm) for improving the adhesion of Au. The reecting plane of the silicon hemicylinder (Harrick Scientic) was cleaned by soaking in hot 1,1,2-trichloroethylene, acetone, and MeOH for 10 min in each, thereafter etching by 1 min treatment in argon saturated 10% HF (aq.). The oxide layer on the surface was removed by soaking in argon saturated 40% NH4F (aq.) for 6 min.30 A thin gold lm was deposited chemically on the cleaned silicon hemicylinder according to a previous report by H. Miyake et al.31 In brief, the reecting plane of the silicon hemicylinder was put into contact with a mixture of 2% HF and a plating solution of 0.015 M KAuCl4 + 0.15 M Na2SO3 + 0.05 M Na2S2O35 H2O + 0.05 M NH4Cl (aq.) (2 : 1 v/v) for 15 minutes at room temperature. The hemicylinder was rinsed with Millipore water to nish the deposition. Deposition of the GO lm Positive charge on substrates, required for GO adsorption, was accomplished by immersing cleaned silicon or gold substrates in 1% (v/v) APTES in EtOH for 30 min32 or in 1 mM MEA in H2O for one hour, respectively. Self-assembled thin lms were deposited on the primed substrates from dilute aqueous GO solutions. For this purpose solid graphite oxide was dispersed in Millipore water (0.51 mg mL1) with the aid of mild ultrasound treatment for 30 min.
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Experimental methods
Chemicals 3-Aminopropyltriethoxysilane (Fluka AG, 96%) (APTES), and 2-mercaptoethylamine hydrochloride (Aldrich, 98%) (MEA) were used for the preparation of self-assembled monolayers. KCl (FF-Chemicals, 99.5%), and NaF (J. T. Baker, Baker analyzed) were used with Millipore water as electrolytes in electrochemical and spectroelectrochemical measurements. The chemical reduction of GO was done with hydrazine monohydrate (Aldrich, 98%). HF (J. T. Baker, 48%), NH4F (Merck, p.a.), potassium tetrachloroaurate (Aldrich, 98%), sodium sulte Na2SO3 (Merck, p.a.), sodium thiosulfate Na2S2O35 H2O (FF-Chemicals, p.a.), and NH4Cl (Acros Organics, 99%) were used in the gold deposition process. 1,1,2-Trichloroethylene (Merck, 99%), MeOH, EtOH were of analytical grade or higher and were used as received for the cleaning of the Si-hemicylinder. Synthesis of GO Natural graphite (SP-1, Bay Carbon) was used for synthesizing the graphite oxide by the modied Hummers method and was further dispersed in water to form GO as previously reported.25 In brief, graphite akes (0.3 g) were chemically oxidized using a mixture of concentrated H2SO4 (2.4 mL), K2S2O8 (0.5 g), and P2O5 (0.5 g) and kept at 80 1C for 4.5 h. This preoxidised product was washed with distilled water to remove all traces of acid and dried. The dried product was dropped into cold (0 1C) concentrated H2SO4 (12 mL). Then, KMnO4 (1.5 g) was slowly added and the temperature of the mixture was kept below 20 1C. After the addition, the solution temperature was kept at 35 1C for 2 h and was diluted with distilled water (25 mL). The mixture was stirred for 2 h; an additional 70 mL of H2O was added to the solution. Shortly after the dilution 2 mL of
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Additionally, the resulting yellow suspension was centrifuged at 4500 rpm (3939g) for 30 min. The pH of the supernatant was set at 2.5 with H2SO4 and used for the thin lm deposition. The adsorption time of 240 min and pH 2.5 of the GO solution were based on a previously reported procedure and on surface plasmon resonance (SPR) measurements (vide infra). Instrumentation The UV-vis spectra of the GO and chemically reduced GO solutions were recorded using a Hewlett-Packard 8453 spectrophotometer. The self-assembly process of GO from dilute aqueous solution was followed by a Texas Instruments Spreeta integrated surface plasmon resonance anity sensor.33 The electrochemical reduction of the thin GO lms on gold electrodes was performed by cyclic voltammetry in deaerated 0.1 M NaF aqueous solutions at a scan rate of 10 mV s1 using a standard calomel reference electrode (+43 mV vs. Ag/AgCl/ 3.5 M KCl reference system) and a platinum wire as an auxiliary electrode. PM-IRRAS dierential reectance spectra and SERS spectra of the thin self-assembled lms on primed gold were measured using a dry-air-purged Nexus 870 FTIR spectrometer (Nicolet) equipped with a Tabletop Optical Module (TOMt) for Nicolett FT-IR spectrometers for polarization modulation experiments and FT-Raman accessory. For each PM-IRRAS spectrum, 4096 scans at 4 cm1 spectral resolution were collected. SEIRAS spectra were measured using the Kretschmann attenuated total reection (ATR) conguration24 in the same TOM conguration as the PM-IRRAS spectra without the polarization modulation of the IR-signal. The p-polarized IR-beam passed at an angle of incidence of 701 relative to the surface normal through a silicon hemicylinder mounted on a homemade spectroelectrochemical cell. The total reected beam from the thin lm was detected using an HgCdTe detector. All IR spectra shown are dierential spectra where the previous spectrum has been used as reference for the following one in the in situ recorded spectral array. SERS spectra were obtained from the thin lms deposited on roughened and primed gold electrodes placed in a homemade spectroelectrochemical cell equipped with a glass window using a Nd:YAG laser at 1064 nm in 1801 backscattering geometry and a germanium detector. For each SEIRAS and SERS spectrum, 1024 scans were collected at constant potential using 4 cm1 spectral resolution. An Ag/AgCl-minireference-electrode (Cypress Systems, Inc., leakfree) and a platinum wire served as reference and counter electrodes. The potentiostat was an EG & G 283 (Princeton Applied Research). Argon purged 0.1 M NaF aqueous solutions were used as an electrolyte. The surface morphology of MEA/GO thin lms on APTES modied silicon was investigated using a Veeco diCaliber AFM instrument (Veeco Instruments Inc.) under ambient conditions in the tapping mode. Rectangular silicon cantilevers (TESPA) of 125 mm length having a resonance frequency of approximately 320 kHz were used. The tip height was 1015 mm and the nominal radius of curvature 8 nm. The raw data obtained were processed by attening and plane tting with the SPMLabAnalysis 7.00 (Veeco Instruments, Inc.) and Gwyddion 2.19 data visualization and analysis software.
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Results and discussion

The adsorption of GO on a MEA primed gold surface was followed by SPR measurements in order to optimize the conditions for the self-assembly process, namely the adsorption time, concentration and pH of the GO deposition solution. The pKa value of the NH2-group in a MEA monomer is close to 7.6,3436 suggesting that the amine group is mainly protonated during the GO adsorption process at pH 6 and 2.5 making the surface positively charged. Attracted by the opposite charge, GO sheets adsorb on top of the MEA layer attached to the gold layer. This self-assembly process is terminated when enough of negatively charged GO platelets are adsorbed on the surface to reverse the surface charge. The change in pH from 6 to 2.5 has an eect on this equilibrium. At pH 2.5, the protonation degree of the NH2-groups of MEA is higher increasing the positive surface charge. On the other hand, the carboxylic acid groups responsible for the negative charge of the GO sheets (surface 2)15 are mostly protonated charge density is 0.4 units per 100 A at this pH, which lowers the negative surface charge density of the platelets. As a result, more GO sheets are required to reverse the surface charge at lower pH which is seen as a greater change in the refractive index of the SPR curves at pH 2.5 in Fig. 1. Additionally, at lower concentrations (but the same pH) less material is adsorbed on the electrode at the same time indicating a diusion limited mass transport process. SPR data revealed that the growth of the GO lm levels-o after ca. 80 min (ca. 15 min at lower concentration). A small drift in the SPR signal after the plateau is comparable to that observed in experiments done with pure solvent and is related to instrumental and other e.g. temperature and diusion eects. Based on this and previously reported results an adsorption time of 240 min, cGO = 0.51 mg mL1 and a pH of 2.5 was chosen.34 Fig. 2a and b show the AFM images of a few layers thick lm of GO on an APTES modied silicon surface after short (30 min) and long (240 minutes) deposition times. The line in the gures indicates the position from where the height proles below the images are obtained. After 30 minutes, the surface is unevenly covered with relatively thin particles whose heights are below 4.0 nm and a few bigger particles with height rising up to 14.4 nm. After 240 minutes, the surface is more evenly covered with GO particles whose heights are below 3.4 nm although

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Fig. 1 SPR curves obtained from a MEA modied gold surface upon interaction with aqueous 0.01 mg mL1 GO suspension at pH 6.0 (&), pH 2.5 (B), and with 1 mg mL1 GO suspension at pH 2.5 (J).

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Fig. 2 The AFM images of Si/APTES/GO (a) after 30, and (b) 240 minutes adsorption time from 0.5 mg mL1 aqueous solution. A line in an AFM image indicates the position of the corresponding height prole.

some regions with higher height proles are visible as well. Both proles indicate lms that are thicker than a single GO layer. The widths of the largest particles are about 150300 nm. The thickness of a single graphene sheet is approx. 0.8 nm26,37 and a GO sheet that contains oxygen-rich defects has a thickness of ca. 1.2 nm.32,3841 According to this the highest spot within a smooth region in our sample would consist of three layers of GO sheets if one considered a sheet thickness of 1.21.3 nm that is in agreement with the above and with the step height of 1.01.3 nm that can be observed in some GO sheets. Generally, the lm is up to ca. 4 nm thick with occasional multilayer GO structures. Importantly, the AFM results show a lm that consists mainly of a few layer GO sheets and occasional multilayer GO particles. It has been reported that intercalated water has a signicant impact on the course of reduction processes in similar kinds of lms,22 which is also conrmed by SEIRAS results (vide infra). Vibrational spectral characterization The PM-IRRAS results of the MEA-primed gold substrate in Fig. 3 show that the asymmetric and symmetric methylene stretching vibrations belonging to a short ethylene chain in the monolayer appear at 2925 and 2856 cm1, respectively. Upon the adsorption of a GO layer the relative intensity of the aforementioned bands increases probably due to the orientation eect of the monolayer. The bulk spectrum of graphite oxide (data not shown) did not reveal any absorption bands at these wavenumbers. An additional broad band around ca. 3300 cm1 is assigned to OH stretching vibrations related to adsorbed water molecules and structural OH groups. In the lower wavenumber range the spectrum of the MEA

monolayer is featureless whereas after GO adsorption several peaks appear below 1800 cm1. The vibration at 1739 cm1 can be related to CQO stretching from carboxylic acid groups. Vibrations belonging to the carboxylate group are seen at 1541 and 1465 cm1. The relative intensity of the CQO absorbance (vs. bulk) has decreased too indicating the ionization of the acidic groups. This is expected because some of the surface groups are to be negatively charged in order to enable a successful adsorption of the GO sheets on the positively charged electrode surface. The band around 1662 cm1 is usually assigned to either the CQC vibrations of the basal plane of graphitic regions or oxygen containing carbon species other than carboxylic acids.42,43 Additionally, the possibility for traces of water remaining in the lm structure, giving rise to absorptions from HOH bending (ca. 1620 cm1), has to be taken into account. Hydroxyl or ether (CO) related vibrations contribute to the weak peak at 1087 cm1.28 In situ spectroelectrochemical characterization of the GO reduction Surface enhanced Raman spectroscopy. Raman spectroscopy represents one frequently used technique for the characterization of carbon-based materials and graphene structures in particular.44,45 The Raman spectra of GO at dierent potentials are shown in Fig. 4a. All Raman spectra exhibit two prominent features, the G-band (B1599 cm1), corresponding to the sp2 lattice, and the D-band (B1305 cm1), which is related to the defects in the sp2 lattice. For a better comparison, all signal intensities are normalized to the G-band (1599 cm1) intensity. From the presented Raman spectra, it is clear that the intensity of the D-band, which is related to disorder structures in the sp2 lattice, is high in graphene oxide (D/G ratio of 1.41 in Fig. 4b) as it exhibits the large abundance of oxygenated functionalities that disrupt the planar sp2 structure. In Fig. 4b, the electrochemical reduction of GO products exhibits D/G ratios between 1.59 (at 0.4 V) and 1.29 (at 1.0 V), suggesting that the order of graphene is partly recovered during the electrochemical

Fig. 3 The PM-IRRAS spectrum of Au/MEA (- - -) and Au/MEA/ GO (___) before the reduction.

Fig. 4 (a) The normalized Raman spectra of the Au/MEA/GO lm as a function of applied potential. The spectra are shifted for clarity. (b) The D/G-intensity ratio as a function of applied potential. (c) The absolute Raman spectra of the Au/MEA/GO lm at 0.0 V before (- - -) and after (___) the reduction. (d) Cyclic voltammogram of Au/MEA/ GO in 0.1 M NaF, a scan rate of 10 mV s1. The arrow indicates the direction of the potential sweep.

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reduction that is consistent with previous reports.46,47 Based on Raman spectra, it is possible to calculate the average crystallite size (La) from the observed D/G ratio.48 The D/G ratio is inversely proportional to the crystallite size and for graphene oxide and electrochemically reduced GO the sizes 16 nm and 15 nm, respectively, have been reported.16 Similarly, an increase in the D/G ratio up to 0.4 V indicates a degradation of the crystallite size after which the size of the graphitic regions grows slightly at higher negative potentials as indicated by the decrease in the D/G ratio. The G band position was shifted by 8 cm1 from 1599 to 1591 cm1 with increasing applied potential. This shift in the G band is in line with the reduction of GO.49 The D band also shows a similar variation in its position from 1305 to 1295 cm1 in Fig. 4c. This is in consistence with the data reported by Ramesha and Sampath from studies in the identical potential range.34 Surface enhanced IR-reection absorption spectroscopy. The reduction of GO to rGO in aqueous solutions was followed spectroelectrochemically during stepwise increase in applied potential towards more negative values between 0 and 1.0 V. Assuming that the spectral treatment and the use of an internal reection set-up compensate the contribution from the environment and the electrolyte in the cell upward extending peaks show the gain and downward extending peaks the loss in the structure of the lm during electrochemical reduction shown in Fig. 5a. The dashed line in Fig. 5a shows the total change in structure induced during the potential cycle. The vibrations related to structural OH groups in GO are overlapped with the vibrations of intercalated and/or free water molecules. A lot of eorts have been made to distinguish between the COH modes originating from a wide range of functional groups on the GO sheets all overlapping in the range of 36003200 cm1.23,50,51 Within the band above 3200 cm1 at least four main vibrations at around 3200 (overtones of scissor vibrations of adsorbed water molecules), 3370 (closely neighbouring hydroxyl groups), 3500 (carboxyl groups of GO), and 3625 cm1 (COH stretch associated with ve-membered-ring lactols and hydroxyl groups of GO from both the basal plane and from the sheet edges) can be distinguished.23,50 The plot in Fig. 5b shows the potential induced change in absorbance of the aforementioned bands at specic potential related to the previous applied potential. The potential induced change in absorbance can be divided into two sections, the rst covering the potential range from 0 to 0.8 V where only a minor increase in the intensity of all the vibration modes takes place. Within this potential range mainly changes in the double layer at the interface between the GO layer and the electrolyte are detected together with the enhancement of the absorbance due to hydrogen bonding interactions (hydrogen bridges) with COH and COOH groups on the GO sheets. These modes are known to be more enhanced in a multilayer lm due to the contribution of intercalated water.22,28,50,52,53 The multilayer nature of the investigated GO lms is also supported by the AFM results in Fig. 2. The reduction of GO involving the conversion of the functional groups starts to take place at potentials more negative than 0.8 V. This is seen as an abrupt change observed above 3200 cm1 where both the width and the intensity of the absorption bands strongly increase. This coincides well with the signicant reduction current increase
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Fig. 5 (a) Dierential SEIRA spectra of the Au/MEA/GO lm in 0.1 M NaF solution; the reference and sample potentials were 0.0 and 0.2 (1), 0.2 and 0.4 (2), 0.4 and 0.6 (3), 0.6 and 0.8 (4), 0.8 and 1.0 V (5) vs. Ag/AgCl, respectively. Curve (6) shows the dierence in absorbance at 0.0 V vs. Ag/AgCl before and after the reduction cycle. (b) The potential dependence of GO (3500 and 3625 cm1) and H2O (3200 and 3370 cm1) related vibrational bands.

observed in the cyclic voltammogram of the GO lm at around 0.8 V vs. Ag/AgCl in Fig. 4d. At 1.0 V nally, a part of the broad band develops a broad negative band with its centre at 3650 cm1 while the rest of the band remains positive. In the lower wavenumber region (Fig. 5a) the same potential dependent increase in absorbance is also seen at 1640 cm1 where a rather broad band is growing. This is the range for the asymmetric vibrational stretching of sp2-hybridized CQC, non-oxidized or reconstructed graphitic domains.10,22 Within this same range also scissor modes of water that are broadened through hydrogen interaction with COH are visible. Additionally also vibrations from edge carbonyl groups might be visible in this region. An additional weak feature arising at 1444 cm1 can be assigned to the deformation vibrations of carboxyl and COH groups (seen only in the spectrum measured upon completion of the potential cycle in Fig. 5a).23 Simultaneously with the abovementioned increasing vibrations, a negative band from vanishing structures appears at around 1220 cm1. The asymmetric shape of the peak at 1224 cm1 indicates that the band consists of several oxygen related vibrations. This is the region for epoxides COC but also for peroxides, ethers, ketones, lactols and benzoquinones.22,28 The response from the intercalated water between the GO sheets resulting in further overlapping in the high wavenumber region in the IR spectra can be compared with the results reported from water in polymer membranes.54 In a LB lm of a polymer, monomeric non-hydrogen-bonded water shows up at 3616 cm1, hydrogen-bonded dimers and small hydrogenbonded clusters have their vibration modes at 3536 cm1 and 3424 cm1. A fourth mode at 3246 cm1 contains a wide
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distribution of hydrogen-stretch vibrations associated with water chains. The eect of hydrogen bonding causing enhancement of the IR intensity as well as the broadening of the OH stretch band is as strongest in the lower wavenumber region in the 36003200 cm1 band, i.e. 34003200 cm1. The electrochemical reduction of epoxides, carboxylates, ethers, etc. has been mostly studied in organic solvents and the reduction potentials reported for these species lie close to each other and are therefore hard to identify in a mixture.55,56 In aqueous solution, the potential window is narrow and the order of easiness of the electrochemical reductions of the dierent functional groups in the GO layers might be due to the access of electrons and the electrolyte to these sites. According to the LerfKlinowski model7 the major components in the basal plane of the GO sheets are epoxide and hydroxyl groups.57,58 The epoxide group can be considered as the most easily reduced functional group in the GO lm.59 The reduction potential of aromatic epoxide groups has been reported to occur around 0.75 to 1.5 V vs. SCE in aqueous solutions.6062 The electrochemical reduction of epoxides CHOCH leads mainly to CHQCH, CH2CH2 or CH2CHOH slightly depending on the medium and its pH where the reduction is made.55 Aromatic carboxylic acids are converted to the corresponding carboxylate anion, aldehyde, alcohol, or hydrocarbon depending on the pH and the number of electrons consumed upon electrochemical reduction.56,63,64 Moreover, in aqueous solutions the formed aldehydes may exist predominantly as the hydrate. The formed hydroxyl groups COH originating from the reduction of the epoxides and carboxyl groups can explain the increase in absorbance intensity at 36003640 cm1 at the beginning of the reduction. The simultaneous reduction of intercalated water contributes to the increase in OH species.

Conclusions
Based on the experimental results obtained from thin GO lms prepared by the self-assembly technique utilizing electrostatic interactions an overview of the potential dependent electrochemical reduction process could be presented. Due to the fact that the redox reactions of the dierent oxygen containing functional groups lie very close to each other a complete identication of each group by potential was not possible by electrochemistry in aqueous solutions. The in situ spectroelectrochemical measurements, however, give a possibility to correlate the specic structural changes with the reduction potential. The role of intercalated water in multilayer GO samples is taken into account in the spectral interpretation. Spectroelectrochemical studies in organic solvents are in progress.

Acknowledgements
Financial support from Academy of Finland (Grant No. 128535) and the Graduate School of Materials Research (JK) is gratefully acknowledged.

Notes and references

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