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Inorganica Chimica Acta 361 (2008) 798–805


A mass spectrometric analysis of sensitizer solution used for dye-sensitized solar cell
Roberto Buscaino a, Claudio Baiocchi b, Claudia Barolo a, Claudio Medana b, Michael Gratzel c, Md. K. Nazeeruddin c, Guido Viscardi a,* ¨

` Dipartimento di Chimica Generale ed Organica Applicata, Center of Excellence for Nanostructured Interfaces and Surfaces, Universita di Torino, Corso Massimo D’Azeglio, 48, 10125 Torino, Italy b ` Dipartimento di Chimica Analitica, Universita di Torino, Via Pietro Giuria, 5, 10125 Torino, Italy c Laboratory for Photonics and Interfaces, Institute of Chemical Sciences and Engineering, School of Basic Sciences, Swiss Federal Institute of Technology, CH-1015 Lausanne, Switzerland Received 6 March 2007; received in revised form 29 May 2007; accepted 8 June 2007 Available online 3 August 2007 Dedicated to Professor Michael Gratzel. ¨

Abstract We report a mass spectrometric study of ruthenium(II) sensitizer ((C4H9)4N)2[Ru(4-carboxy-4 0 -carboxylate-2,2 0 bipyridine)2(NCS)2] (N719) in various organic and aqueous solvents. At the equilibrium different species were found, depending on solution properties. After stoichiometry confirmation through high-resolution mass spectra and isotopic pattern analysis, the formation of these complexes was found to strongly depend from the polarity and the ionic strength of solvent medium. Mass spectra obtained in acetonitrile/tert-butanol (1:1) mixture, used for the absorption of N719 on TiO2, suggests that the main species involved in the adsorption process is the dicarboxylate form of N719 with one (C4H9)4N as counter ion. The photovoltaic data of the N719 sensitizer adsorbed on TiO2 films exhibited a remarkable power conversion efficiency, 11.20% at 1 sun. Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Ru(II) complex; ESI-MS; Noncovalent complexes; N719 sensitizer; Dye-sensitized solar cell

1. Introduction Dye-sensitized solar cells are currently attracting widespread academic and commercial interest for conversion of sunlight into electricity because of its low cost and high efficiency [1–23]. At the heart of the system is a mesoporous oxide layer composed of nanometer-sized particles, and the sensitizer, which allows electronic conduction and harvesting of solar radiation, respectively. Various ruthenium complexes containing anchoring groups such as carboxylic acid, dihydroxy, and phosphonic acid on pyridine ligands have been used as sensitizers [24]. The anchoring groups serve to immobilize the sensitizer onto nanocrystalline

Corresponding author. Tel.: +39 0 116707598; fax: +39 0 116707591. E-mail address: (G. Viscardi).

TiO2 surface, which upon photoexcitation injects electrons into the TiO2 conduction band and the concomitant hole transfer to the redox electrolyte [25,26]. The anchoring groups of the sensitizer that contain protons, upon adsorption, transfer most of its protons to the TiO2 surface charging it positively and thereby the Fermi level moves down (positively). However, the positive shift of the Fermi level decreases the gap between the redox couple iodide/triiodide and the Fermi level, resulting in lower open-circuit potential. On the other hand, if the sensitizer carries zero protons, then the Fermi level moves negatively, due to adsorption of anionic complex, and the cations thereby have a higher value for open-circuit potential while that of short circuit current is low [27–29]. Therefore, there should be an optimal degree of protonation of the sensitizer for which the product of short circuit photocurrent

0020-1693/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.ica.2007.07.016

25 (KV). Recently. (N719). confirming N719 purity (Fig.1 N. The solution at basic pH was obtained by adding to aqueous solution some drops of a 30% ammonium hydroxide solution to obtain a concentration solution of 0.3 using 0. ESI (Electro Spray Ionization) experiments were conducted with a Thermo Finnigan Advantage Max Ion trap spectrometer in negative ion acquiring mode. Its stoichiometry is confirmed by isotopic pattern as shown in Fig. 3b are reported experimental and calculated isotopic pattern of peak at m/z 704. The same purification procedure was repeated two more times to get pure Nbonded isomer complex. and water/acetonitrile 1:1. High-resolution spectra were recorded on an LTQ Orbitrap Hybrid Mass Spectrometer. The complicate fragmentation obtained in MS/MS spectrum revealed that the interactions between the Ru(II) centre and the two bipyridine ligands are very strong. Spectral homogeneity across the peak evidences that no coelution occurred.2 0 bipyridine)2(NCS)2] (N719) sensitized TiO2 solar cell can be related to several factors. Then. auxiliary gas flow rate at 5 (arbitrary unit).5. cis-Dithiocyanatobis(4-carboxy-4 0 -carboxylate-2. Results and discussion Purified N719 was analysed by HPLC using a diode array as detector.8 mg of complex in 10 ml of acetonitrile/tert-butanol (1:1). Structure of complex was confirmed by the integration ratio of aliphatic and aromatic 1H NMR signals and elemental analyses [32]. / Inorganica Chimica Acta 361 (2008) 798–805 799 and open circuit potential is high that determines the power conversion efficiency of the cell. Buscaino et al. 1a. sheath gas flow rate was set at 25 (arbitrary unit). and (iii) an aqueous solution of 5 mM ammonium acetate added with 5% of methanol. relatively long-lived excited states. such as broad range of visible light absorption.9. It is adsorbed on mesoporous anatase TiO2 as tetrabutylammonium double salt from a solution of acetonitrile/tert-butanol (1:1) mixture. 3a. After allowing flask to 25 °C.R. Experimental HPLC analyses were performed on a Shimadzu HPLC 10-AVP series equipped with a photodiode array SPD-M 10 Avp as a detector using as solid phase a Luna C-18 (2) column 4. Mass Spectrometry with ESI interface appeared particularly useful because [33] (i) it can directly detect mono and multicharged ion. The chromatographic purification of N719 was carried out three times on a column of Sephadex LH-20 using the following procedure. (ii) does not alter the connectivity of the complex through disassembly/reassembly sequences and (iii) causes essentially no or very little fragmentation. In this paper. A mother solution of N719 in acetonitrile/tert-butanol (1:1) was prepared at the same concentration of that used for the adsorption on TiO2. 3. and tube lens offset at À60. 1 ml of the mother solution was diluted to 10 ml by adding (i) acetonitrile/tert-butanol (1:1) mixture. On this peak tandem mass spectrometry analysis was performed in order to obtain more structural informations. The high performance achieved using ((C4H9)4N)2[Ru(4-carboxy-4 0 -carboxylate-2. solvents used for MS analysis were purchased from Aldrich and were used without further purification. It is therefore important to analyze in detail the structure of the sensitizer from adsorbing solution in order to design and develop tailored sensitizers. obtained by solving 13. capillary temperature at 270 °C. and the effect of protons and the cations carried by the sensitizer. added with 0.9 and at m/z 1187. Newkome and Wesdemiotis applied this technique to study organometallic assemblies containing bisterpyridinyl-Ru(II) connectivity [34]. 1b). the precipitated complex was collected on a glass frit and air dried. pH was monitored using a pH-metre Crison Basic 20 equipped with a glass electrode Crison 5202. reported in Fig. The assignation of the small peak at m/z 704.31]. The concentrated solution was filtered through a sintered glass crucible and charged onto a Sephadex LH-20 column. 2. (ii) 5% aqueous methanol solution. capillary voltage at À7 (V). The synthesis of N719 sensitizer was reported in our previous paper [10. Solvents of relative lipophilic character favour the dissociation of one of the two ion pairs of N719 complex. HPLC run. then diluted 1:10 to obtain a concentration useful to record mass spectrum by direct injection method.1 and two minor peaks at m/z 704. Nitrogen was used as sheath and auxiliary gases. which was prepared in water. The N719 complex was dissolved in water containing 2 equiv of tetrabutylammonium hydroxide. we report detailed HPLC (High Pressure Liquid Chromatography) and mass analysis of the N719 sensitizer. and the mono-anion (E) (Scheme 1) is mainly observed. its excited energy almost matching those of TiO2 conduction band.02 M HNO3 acid. Sprayed solutions were prepared starting from a mother solution. solvating the hydrophobic TBA cation. corresponding to the mono-anion . The main band was collected and the solution pH was lowered to 4. In order to characterize charged complexes involved during N719 adsorption on TiO2 surface.6 mm · 250 mm with a particle size of 5 lm. The interaction between the solid phase and the TBA counterions of the Ru(II) complex is responsible for the tailored shape of the peak. The titration was carried out slowly over a period of 3 h. shows only one peak. the solution was kept at À20 °C for 15 h.1% of formic acid as liquid phase. 2 shows a major peak at m/z 946. The mass spectrum reported in Fig. The two hydrophobic cations were used in order to increase the solubility of sensitizer in organic solvent. The adsorbed complex was eluted using water. In Fig. is a high performance sensitizer in Gratzel photovoltaic ¨ cells [30].2 0 -bipyridine)ruthenium(II) ditetrabutylammonium salt. the reported working pH-range is 0–12. at a flow rate of 1 ml/min.00 (V). spray voltage at 3.9 required the use of high resolution mass spectrometry technique.

However. Moreover. To confirm that the observed species were not instrumental artefact. we tried to decrease the ion count within the ion trap. Ru(II) complex (B) (Scheme 1) with no counterion. Buscaino et al.800 R. ESI spectrum of N719 Ru(II) complex in tert-butanol/acetonitrile solution (1:1). . Fig. The dissociation of both ion couples would give an unstable di-anion: extraction of a hydrogen atom from the protic solvent gives a more stable tricarboxylic mono-anion complex (B) (Scheme 1). species evidenced in normal analysis conditions were still observed. (a) HPLC analysis and (b) UV–visible spectrum at peak maximum of N719 Ru(II) complex. solutions were monitored for about 48 h and no changes were observed indicating that equilibria among stable species in different solutions are reached within few minutes. if observed species were created in the mass analyzer they probably disappear. in our case. In this way. 2. 1. / Inorganica Chimica Acta 361 (2008) 798–805 Fig.

attributed to species (D) (Scheme 1).21 z = 2 m/z: 472. the peak at m/z 1187. ESI analysis evidenced a peak at m/z 1187. So.8. The addition of methanol is necessary to assist water evaporation during ESI experiments.22 NCS (A) NCS 2x O O O O N (B) N719 C58H86N8O8RuS2 Exact Mass: 1188. Along with the main peak at m/z 946.51 O N N NCS Ru N NCS N O HO O (F) O C26H15N6O8RuS2Exact Mass: 704. Solvation of TBA in water is not so effective as in tert-butanol/acetonitrile. corresponding to tetra-carboxylate species with three TBA counterions (G) (Scheme 1). appears.R. and a less intense peak at m/z 593. As a consequence.8.9 presented some difficulties.5 O O O N Ru N O O O O N NCS N NCS O 3x N (G) C74H120N9O8RuS2Exact Mass: 1428. The assignation of peak at m/z 473.49 z = 2 m/z: 593. increases and the small peak at m/z 1428. . The use of solvent systems with different polarity can be useful to evidence that minor species are not impurities but members of the Ru(II) complex-TBA acid–base equilibrium.78 Scheme 1. N719 Ru(II) complex species observed in solution by ESI experiments.2.2 and a very small peak at m/z 1428. 5a).1. becomes observable and its stoichiometry is confirmed by isotopic pattern (Fig. / Inorganica Chimica Acta 361 (2008) 798–805 801 O O O N Ru N O N O OH O N Ru N O O O O HO O O N Ru N O O OH HO O N Ru N O OH HO O N NCS N NCS O O N N N NCS N NCS O O O N N O 2x N NCS (D) NCS N O O OH O (C) C58H84N8O8RuS22Exact Mass: 1186. and the organic cation tends to form the ion pair with the carboxylic group.94 C58H85N8O8RuS2Exact Mass: 1187.24 O N N NCS Ru N NCS N OH O O (E) O C42H49N7O8RuS22Exact Mass: 945.61 O 2x N C42H50N7O8RuS2Exact Mass: 946. The higher polarity of solution also favours the formation of doublecharged anions. 4 shows the mass spectrum of N719 complex in a solution obtained by diluting 1 ml of mother solution in acetonitrile/tert-butanol (1:1) with 9 ml of a 5% aqueous methanol solution.5. Fig. Buscaino et al. corresponding to tri-carboxylate species with two TBA counterions (F) (Scheme 1). the peak at m/z 593.5 of comparable intensity with the former.

three peaks at m/z 946.1 z = 1 and (b) experimental (top) and calculated (bottom) patterns of peak at m/z 704. (a) Experimental (top) and calculated (bottom) patterns of peak at m/z 946.802 R. 4. 6). in particular. Fig. To verify the assignment with higher accuracy. we could evaluate the intensity of TBAcarboxylate interaction monitoring the occurring of exchange reaction between TBA. Using this volatile salt we were able to study the effect of an increase in ionic strength of solvent medium.9 z = 1 of N719 Ru(II) complex in tert-butanol/acetonitrile solution (1:1). / Inorganica Chimica Acta 361 (2008) 798–805 Fig.8) suggests that the presence of electrolyte favours the association of the .5 and 1428. 5b and confirms the formation of compound (C).8 appeared with a ratio of about 1:1:1.6 but the overlay of isotopic peaks separated by a half mass unit (z = 2) with similar mass signals generates an apparent mass shift. we performed an analysis with a high resolution instrument. 3.1. and the ammonium cation of electrolyte. ESI spectrum of N719 Ru(II) complex in water added with 5% of methanol. Under these conditions. Buscaino et al. Spectra at high resolution (R = 80 000). isotopic pattern of this peak. counter ion of the Ru(II) complex. obtained with low resolution mass instrument. 6. The addition of 5 mM ammonium acetate to the above aqueous solution once more brought changes in mass spec- trum (Fig. The obtained isotopic pattern is reported in Fig. of species G (m/z 1428. The marked increase of stability of species F and. as evidenced in Fig. 1187. Moreover. suggested the presence of compound (C) with z = 2 and exact mass 472.

as confirmed by the prevalence of peak at m/z 1428. ESI analysis is reported. we set at 11 the pH value of the diluted aqueous (5% methanol) solution adding ammonium hydroxide to obtain 0. Fig.1 N solution. ESI spectrum of N719 Ru(II) complex in ammonium acetate solution added with 5% of methanol. The photocurrent . 8. In Fig. 7a and b. species F and G.2 z = 2. Buscaino et al. The base induces the dissociation of carboxylic groups. suggesting the formation of a strong ion pair between Ru(II) complex and TBA. No peaks due to ammonium/TBA exchange are detectable. To further confirm the behaviour of TBA in polar solvent system. (a) Experimental (top) and calculated (bottom) patterns of peak at m/z 593. 5. Also in this case the isotopic pattern analysis. (b) experimental (top) and calculated (bottom) patterns of peak at m/z 472. The concentration of the dye solution was typically 5 · 10À4 M and the electrodes were dipped for 18–20 h. confirms. / Inorganica Chimica Acta 361 (2008) 798–805 803 Fig. lypophilic TBA to carboxylate. respectively. and ammonium species occurred.R. reported in Fig. counter ion of the Ru(II) complex.8 stabilized with the formation of three strong ion pairs.6 z = 2 of N719 Ru(II) complex in water added with 5% of methanol. The N719 dye solution containing the monoprotonated species was prepared in 1:1 CH3CN + tert-BuOH solution mixture by adding 1 equiv of tetrabutylammonium chenodeoxycholic acid salt to the dye solution. 6. The isotopic patterns confirm peaks assignation. Spectra at high resolution (R = 80 000). Also in this case no exchange reaction between TBA.

(a) Experimental (top) and calculated (bottom) patterns of peak at m/z 1187.5 solar conditions (1 sun).5. 4. The study in acetonitrile/tert-butanol (1:1) mixture. Conclusions The sensitizer N719 was synthesised and purified at chromatographic grade.5 mA current. / Inorganica Chimica Acta 361 (2008) 798–805 Fig. the mono-protonated N719 sensitized solar cell exhibited 17.75 (area of the cell: 0. Fig.73 ± 0. Different and stable species in fast-established equilibria were analysed in solution by mass spectrometry in electrospray ionization (ESI) and identified through the exam of the isotopic patterns. evidenced that the main species involved in the adsorption process is a dicarboxylate .8 of N719 Ru(II) complex in aqueous ammonium acetate 5 mM solution added with 5% of methanol. 846 mV potential and fill factor 0.804 R.20%. used for the adsorption on TiO2. Buscaino et al. (b) experimental (top) and calculated (bottom) patterns of peak at m/z 1428. 8. The incident monochromatic photon-to-current conversion efficiency (IPCE) plotted as a function of excitation wavelength exhibits a value of 87% in the plateau region. Under a standard global AM 1. pH set at 12 by the addition of ammonium hydroxide. ESI spectrum of N719 Ru(II) complex in water added with 5% of methanol.158 cm2) yielding an overall conversion efficiency of 11. 7. action spectra of the N719 sensitizer show broad featurescovering a large part of the visible spectrum.

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