Supporting information. For. In-situ Identification of Intermediates of Benzyl. Coupled with DFT Calculation
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1 Supporting information For In-situ Identification of Intermediates of Benzyl Chloride Reduction at a Silver Electrode by SERS- Coupled with DFT Calculation An Wang, Yi-Fan Huang, Ujjal Kumar Sur, De-Yin Wu, Bin Ren, Sandra Rondinini, Christian Amatore*, and Zhong-Qun Tian * * s: zqtian@xmu.edu.cn, christian.amatore@ens.fr 1. Desorption of chloride ion as the product from the surface Since chloride anion is one necessary product of any overall two-electron reduction sequence for benzyl chloride at silver electrodes, [1] previous works suggested that its interaction with the silver surface may play a significant role in the overall catalytic effect displayed by silver cathodes. [2] Previous capacitance measurements performed with KCl (0.5 mm in acetonitrile) had evidenced that chloride ions adsorb onto polycrystalline silver electrodes over the positive part of the potential range. [2] However, in the present study the characteristic potential dependent Ag-Cl vibrational band [3] located at about cm -1 could not be observed in the presence of benzyl chloride reduction over the wide negative potential range encompassing the voltammetric wave (see Fig. 1b). In order to confirm it, we performed the SERS measurement with KCl (0.5 mm in acetonitrile) without benzyl chloride in a wide S1
2 potential region from -0 V to -1.8 V. It was evidenced that chloride ions adsorb onto the silver electrode only in the positive part of the potential range, they desorbed from the surface in the potential region negative of -1.0 V. It is inferred that under our present conditions and those described previously for the same reaction the surface coverage of chloride ions must be much smaller than expected from previous investigations. [2] This is certainly due to the strong electrostatic repulsive force from the negatively charged surface and to the occurrence of strong competitions by nitrile species and benzyl intermediates (see text and below) strongly adsorbed at the silver surface. 2. DFT calculation Details Cluster models including silver clusters with different sizes of Ag n (n = 1~5, 10) were used in the DFT computations to simulate the silver electrode surface for optimizing the structures of surface complexes of possible intermediates and products. DFT calculations were performed with the hybrid exchange functional of Becke s 3 parameters (B3) and the Lee-Yang-Parr s nonlocal correlation functional (LYP) for finding the stable optimization geometries and calculating vibration Raman spectra. [4, 5] The basis sets for C, Cl and H were G** with polarization functions for C, Cl and H, and with diffuse function only for C and Cl atoms. For silver atoms, the valence and core electrons were described by the basis set of LanL2DZ and the corresponding relativistic effective core potential (ECP), respectively. [4] The solvent effect was considered by the integral equation formal polarization continuum model (IEF-PCM). [6] All the calculations concerning the geometry optimization and the Raman spectra were performed by using Gaussian09 software package. [7] For comparison of theoretical and experimental data, all the calculated frequencies were scaled by a factor 0.98 due to the correction of the harmonic approximation and the incomplete DFT approaches. The intensities of the Raman bands were estimated by calculating the differential Raman scattering cross section. [8] To optimize the configurations and calculate Raman spectra of benzyl-ag n and its anionic clusters, we first studied the cluster effect on the calculation by utilizing a series of clusters containing various silver atoms as shown in Figs. S1s & S2. It can be seen that the spectral feature did not change drastically S2
3 upon varying the silver clusters size from Ag 3 through Ag 5 to Ag 10. Accordingly, a Ag 4 cluster was used in the present study to analyze the spectra of the benzyl-silver adduct at the potential region ranging from -1.2 V to -1.6 V. Figure S1 The configurations and calculated Raman spectra of benzyl-ag n (n = 1~5,10). S3
4 Figure S2 The configurations and calculated Raman spectra of benzyl-ag n (anion) (n = 1~5, 10). The coordinates of benzyl radical Ag 4 adduct and benzyl anion Ag 4 adduct shown in Fig. 2d & e are given below. Benzyl-Ag 4 (neutral) S4
5 X Y Z C C C Benzyl-Ag 4 (anion): C C C C H H H H H H H Ag Ag Ag Ag S5
6 X Y Z C C C C C C C H H H H H H H Ag Ag Ag Ag Vibrational assignments on the most intense bands Figures S3 & S4 show the vibrational assignments of four most intense bands in the SERS spectra according to the experimental and theoretical results. Since the benzyl radical or benzyl anion adsorb on the surface in a titled configuration, the intense SERS bands correspond to the C-Ag stretch, the out-of- S6
7 plane ring C-H bend, and two combining modes of the CH 2 wagging vibration and the out-of-plane ring C-H bend vibrations. The vibrational modes at 862 cm -1 and 898 cm -1 for the neutral species and 850 cm -1 and 884 cm -1 for the anionic species may correspond to the most intense and broad SERS band observed at around -1.4 V (vide infra). Figure S3 The assignments on four vibrational modes of benzyl-ag 4 based on DFT calculation. Figure S4 The assignments on four vibrational modes of benzyl-ag 4 -anion based on DFT calculation. S7
8 5. The analysis of the strongest peak at around 800 cm -1 In order to unambiguously identify the reaction intermediates at the potentials around -1.4 V, it was essential to analyze the most intense and broad SERS peak observed at around 800 cm -1 in this potential region (see Fig. 1b). As this peak was unusually broad it must have resulted from the overlap of several bands. In order to identify the underlying individual bands we relied on curve fitting. The red line in Fig. 5s represents the experimental spectrum at -1.4 V, the green ones are the individual spectra fitted by software, and the blue curve is the addition of the fitting spectrum. According to this analysis, the broad peak observed at around 800 cm -1 consisted of four peaks, i.e., 790, 821, 853 and 884 cm -1. Compared with the spectra in Fig. 2d, e and f, we may conclude that the spectrum at -1.4 V is in fact the superimpositions of two spectra of benzyl radical-ag adduct and benzyl anion-ag adduct. This clearly indicates that there are two reaction intermediates generated from the electrode simultaneously. When the potential was moved to -1.6 V, this broad peak was changed to a narrow one (see Fig. 1b). The band frequency implies that the benzyl anion-ag adduct is dominant at the more negatively charged surface. Figure S5 The curve fitting of the spectrum recorded at -1.4 V. In order to correlate two coexisted surface species with the spectral feature obtained experimentally, a series of spectra composed by calculated spectra of neutral and anionic benzyl-ag 4 adduct in various ratios were analyzed as shown in Figure S6. It can be seen that the spectrum with the ratio of 5:1 shows a relatively similar spectral profile at the characteristic band at ca. 800 cm -1. It may infer that the S8
9 anionic benzyl species is dominant at the surface at -1.4 V. When the potential was stepped to -1.6 V, the experimental spectrum shows that the band width of the 800 cm -1 band decreases distinctly in comparison with that at -1.4 V. This trend is similar to the simulation result as the ratio of the anionic to neutral benzyl-ag 4 adduct changes from 5:1 to 10:1. It confirms the reduction of neutral benzyl-ag 4 adduct to the anionic one as discussed in the main-text. The consistency between the experimental and theoretical fitting results shows that the SERS-DFT study is helpful to analyze the transformation of reaction intermediate from neutral to anionic benzyl-ag 4 adduct upon the potential change. Figure S6. The fitting spectra on the experimental data at -1.4 V composed by various ratios of neutral and anionic benzyl-ag 4 adduct. It should be noted that at the present stage, our DFT calculation is not able to fit the experimental spectra perfectly. It has been well known that so far there has still been a problem to build a perfect model to simulate the complicated electrochemical interface due to the limitation of the ability of the computer speed and the calculation method. However, in comparison with many other Raman-DFT works, our result could be good enough to ensure our assignment is correct. The DFT simulation gives four groups of Raman bands in the regions at around 530 cm-1, 800 cm-1, 1100 cm-1 and 1200 cm-1, which fits the experimental result well as shown in Fig. 2. The reason of the relatively large deviation of S9
10 the main peak at about 800 cm -1 is that this wagging vibrational mode of the =CH 2 group is one of the groups most close to the surface (it is this carbon atom to bind to the surface). So this particular vibration is influenced strongly by the complex environment, such as the co-adsorbed acetonitrile, heterogeneous arrangement of surface atoms and applied potential distribution. This is also the reason why this band is much broad than other bands but similar to the Ag-C band that is also broad. Although we have considered the solvent effect in our DFT calculation, we cannot account for other complicated factors caused by the complex structure near the surface. As a consequence, the main peaks are at 850 and 884 cm -1 in the simulation that does not catch the main peak at 790 cm -1 well. 6. Discussion on possible products At the potentials more negative than -1.8 V, we looked particularly for the presence of the two previously reported organic electrolytic products which are follow-up products arising from the intrinsic reactivity of free benzyl anions, [1] viz., toluene and 3-phenylpropanenitrile (Eqns (1+2)). We also investigated for the possible presence of 1,2-diphenylethane (Eqn (3)). PhCH CH 3 CN PhCH CH 2 CN (1) - CH 2 CN + PhCH 2 Cl PhCH 2 CH 2 CN + Cl - (2) PhCH PhCH 2 Cl PhCH 2 CH 2 Ph + Cl - (3) PhCH MH PhCH 3 + M - (4) where MH = TEAP or residual water. S10
11 Figure S7 a) Experimental SERS spectrum at -1.8 V and calculated Raman spectra for possible reaction products: b) toluene, c) 3-phenylpropanenitrile, d) 1,2-diphenylethane The DFT-predicted spectra for toluene (Figure S7b) or 1,2-diphenylethane (Figure S7d) do not match at all the experimental spectrum. This may seem surprising since toluene is the major product observed in electrolyses. [1] It should be noted that both species are not expected to give rise to any significant interactions with a silver surface. Hence, whenever formed they should then immediately diffuse away from the electrode surface so that their SERS have to be negligible irrespective of their electrolysis yields. [1] Conversely, with some allowance for distortions due to strong adsorption on the silver surface, the vibrational spectrum predicted for the 3-phenylpropanenitrile (Figure S7c) matched reasonably well with the experimental one (Figure S7a). Though this compound was a minor one compared to toluene (ca. 20% relative yield) [1] it could nevertheless be detected by SERS due to its strong binding onto the silver surface via its nitrile moiety. This may serve as a caveat in the discussion of the SERS results obtained in the present investigation since any species giving rise to a strong binding at the silver S11
12 surface may prevent competitively weakly bound ones to provide observable SERS signatures (e.g., as for the surprising absence of any chloride-silver adduct [2] in SERS spectra). Nevertheless, the observation of 3-phenylpropanenitrile which may only result from a SN 2 reaction between benzyl chloride and the acetonitrile anion (Eqn (2)), [1] militates for the intermediate formation of a fleeting benzyl anion during time scales that are compatible with the voltammetric ones. The same is true for toluene whose formation is a necessary requirement for that of 3-phenylpropanenitrile (Eqns (1,2)). 7. Full reference of ref. [11] [11] Gaussian09 (RevisionA.02): Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J. and Fox, D. J. Gaussian, Inc., Wallingford CT, Gaussian 09, Revision A.02. Wallingford CT, Experimental details All the electrochemical experiments were carried out at silver wires (2 mm diameter; % from Alfa Aesar), which were sealed into a Teflon (polytetrafluoroethylene) stick. The electrode was polished to a mirror finish with emery paper of decreasing grain size followed by alumina powder with 3, 1 and 0.3 μm particle sizes in this sequence. The SERS active electrode was prepared by the special S12
13 oxidation-reduction cycle (ORC) method. [9] The solution (CH 3 CN M TEAP + 5 mm PhCH 2 Cl) was sealed in a electrochemical-sers (EC-SERS) Raman cell. Raman spectra were obtained using Labram 1 confocal microprobe Raman system (Jobin-Yvon, France) using a nm He-Ne exciting laser. The EC-SERS cell consisted of SERS active Ag as the working electrode, a Pt wire ring as the counter electrode and an Ag/Ag + electrode as the pseudo-reference electrode. For convenience the potential scale has been converted to a potential referred to the saturate calomel electrode (SCE) by subtracting a potential difference of ~45 mv. During the in-situ EC-SERS experiments, the Raman spectrometer was synchronized with a potentiostat to control the potential of the working silver electrode. An optically transparent quartz window was used to protect the solution or electrode being contaminated by the ambient atmosphere. When using non-aqueous solvents like acetonitrile in the present work, the cell was equipped with an O-ring to perform under liquid and gas tight conditions. In the case of potential dependent EC-SERS experiments (Figure 1 in the communication) each spectrum was recorded with a 1 s integration time. Figure S7 Illustration of the experimental setup of electrochemical SERS. References : [1] Isse, A. A.; Gottardello, S.; Maccato, C.; Gennaro, A. Electrochem. Commun. 2006, 8, 1707 [2] Ardizzone, S.; Cappelletti, G.; Mussini, P.R.; Rondinini, S.; Doubova, L. M. J. Electroanal. S13
14 Chem. 2002, 532, 285. [3] Mattei, G. ; Quagliano, L. G. ; Pagannone, M. Europhys. Lett. 1990, 11, [4] Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. [5] P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 299. [6] a) Cancès, M. T.; Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997, 107, 3032; b) Cossi, M.; Barone, V.; Mennucci, B.; Tomasi, J. Chem. Phys. Lett. 1998, 286, 253; c) Mennucci, B.; Tomasi, J. J. Chem. Phys. 1997, 106, [7] Gaussian09 (RevisionA.02): Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J. and Fox, D. J. Gaussian, Inc., Wallingford CT, Gaussian 09, Revision A.02. Wallingford CT, 2004 [8] Wu, D.Y.; Liu, X.M.; Duan, S.; Xu, X.; Ren, B.; Tian, Z.Q. J. Phys. Chem. C 2008, 112, [9] Funtikov, A. M.; Sigalaev, S. K.; Kazarinov, V. E. J. Electroanal. Chem. 1987, 228,197. S14
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