Spectroelectrochemistry of Electrochromic and electroluminescent substances shows a strong correlation between electrochemical reactions on electrodes and changes in absorbance or luminescence adjacent to the electrode. This was demonstrated by the well-known substances methylviologen and tris (2,2’-bipyridyl) dichloro-ruthenium [Ru (bpy)3]2+. The experimental setup used a conventional potent iostat connected to a fiber spectrometer. Different commercial spectroelectrochemical cells were used: A thin-film absorption cell with a platinum mesh working electrode and as pecular reflection/transmission cell with different screen-printed electrodes. For luminescence measurements, a conventional quartz cuvette with the platinum mesh electrode was used. All cells were inserted into commercial cell holders with connectors for optical fibers. Spectroelectrochemistry becomes increasingly important as an analytical method. In addition, the empirically observed didactical problems of misunderstanding electrochemical electrode reactions can be overcome by visualizing the electrode processes in spectroelectrochemical measurements. The procedures followed in these experiments were designed for typical undergraduate students in electrochemistry.
| [1] | Heineman, W. R. Spectroelectrochemistry. J. Chem. Educ. 1983, 60, (4). 305-308.View Article |
| [2] | Monk, P. M. S, The Viologens, Wiley, Chichester, 1998. |
| [3] | Monk, P. M. S.; Mortimer, R. J.; Rosseinsky, D. R. Electrochromism and Electrochromic Devices, Cambridge University Press, Cambridge, 2007.View Article |
| [4] | Granquist, C. G.; Pehlivan, I. B.; Green, S. V.; Lansaker, P. C.; Niklasson, G. A, Oxide-based Electrochromism: Advances in materials and devices, Mater. Res. Soc. Symp. Proc. 2011, 1328, 11-22.View Article |
| [5] | Pang, Y.; Chen, Q.; Shen, X.; Tang, L.; Qian, H, Size-controlled Ag nanoparticle modified WO3 composite films for adjustment of electrochromic properties, Thin Solid Films, 2010, 518, 1920-1924.View Article |
| [6] | Galiote, N. A.; Parreira, R. L. T.; Rosolen, J. M.; Huguenin, F.Self-assembled films from WO3: Electrochromism and lithium ion diffusion, Electrochem. Commun., 2010, 12, 733-736.View Article |
| [7] | Hepel, M. Electrochromic WO3 Films: Nanotechnology Experiments in Instrumental Analysis and Physical Chemistry Laboratories, J. Chem. Educ., 2008, 85, 125-127.View Article |
| [8] | Duek, E. A. R.; De Paoli, M. A. Mastragostino, M, An electrochromic device based on polyaniline and Prussian blue, Adv. Mater., 1992,4, 287-291.View Article |
| [9] | Jelle, B. P.; Hagen, G.Transmission spectra of an electrochromic window based on polyaniline, Prussian blue and tungsten oxide, J. Electrochem. Soc., 1993, 140, 3560-3564.View Article |
| [10] | Barbero, C.; Miras, M. C.; Koetz, R.; Haas, O.Comparative study of the ion exchange and electrochemical properties of sulfonated polyaniline (SPAN) and polyaniline (PANI), Synth. Met., 1993, 55, 1539-1544.View Article |
| [11] | Ram, M. K.; Maccioni, E.; Nicolini, C.The electrochromic response of polyaniline and its copolymeric systems, Thin Solid Films, 1997, 303, 27-33.View Article |
| [12] | Beden, B.; Enea, O.; Hahn, F.; Lamy, C. Investigations of the absorption of Methyl Viologen on a platinum electrode by voltammetry coupled with “in situ” UV-visible reflectance spectroscopy, J. Electroanal. Chem., 1984, 170, 357-361.View Article |
| [13] | Bird, C. L.; Kuhn, A. T. Electrochemistry of the Viologens, Chem. Soc. Rev., 1981, 10, 49-82.View Article |
| [14] | Barclay, D. J.; Bird, C. L.; Martin, D. H. Speed considerations for electrochromic displays, J. Electron. Mater.1979, 8, 311-315.View Article |
| [15] | Ruff, A.; Speiser, B.; Dreiling, J. Redox-active silica nanoparticles. Part 7. Redox behavior of core/shell structured viologen modified silica particles immobilized at paraffin impregnated graphite electrodes, J. Electroanal. Chem., 2013, 710, 10-16.View Article |
| [16] | Passon, M.; Ruff, A.; Schuler, P.; Speiser B.; Dreiling, J. Redox-active Silica Nanoparticles. Part 8. Stepwise solid-phase synthesis and solid state electrochemistry of redox active viologen core/shell structured modified silica materials, Chem Electro Chem, 2014, 1, 263-280.View Article |
| [17] | Saricayir, H.; Uce, M.; Koca, A. In Situ Techniques for Monitoring Electrochromism, J. Chem. Educ.2010, 87, 205-207.View Article |
| [18] | Monk, P. M. S.; Turner, C.; Akhtar, S. P. Electrochemical behavior of methyl viologen in a matrix of paper, Electrochim. Acta, 1999, 44, 4817-4826.View Article |
| [19] | Rueda, M.; Compton, R. G.; Alden, J. A. Prieto, F. Impedance voltammetry of electro-dimerization mechanisms: Application to the reduction of the methyl viologen di-cation at mercury electrodes and aqueous solutions, Electroanal. Chem. 1998, 443, 227-235.View Article |
| [20] | Gerardi, R.D.; Barnett, N.W.; Lewis, S.W. Analytical applications of tris (2,2'-bipyridyl) ruthenium(III) as a chemiluminescent reagent. Analyt.Chim.Acta,1999, 378, 1-43.View Article |
| [21] | Martin-Yerga, D.; Perez-Junquera, A.; Hernandez-Santos, D.; Fanjul-Bolado, P. Electroluminescence of [Ru(bpy)3]2+ at gold and silver screen-printed electrodes followed by real-time spectroelectrochemistry, Phys. Chem. Chem. Phys. 2017, 19, 22633-22637.View Article PubMed |
| [22] | Costin, J. W.; Barnett, N. W.; Lewis, S. W. Determination of proline in wine using flow injection analysis with tris (2, 2’-bipyridyl) ruthenium (II) chemiluminescence detection, Talanta 2004, 64, 894-898.View Article PubMed |
| [23] | Habekost, A. Investigations of Some Reliable Electrochemi luminescence Systems on the Basis of tris (bipyridyl) Ruthenium (II) for HPLC Analysis. World J. Chem. Educ. 2016, 4, 13-20. |
| [24] | Forslund, B. A. Simple Laboratory Demonstration of Electrochromism, J. Chem. Educ.,1997, 74, 962 - 963.View Article |
| [25] | Abdinejad, T.; Zamanloo, M.R.; Alizadeh, T.; Mahmoodi, N. O.; Pouran S. R. Photochromic and Electrochromic Diimide Synthesized Simply from Inexpensive Compounds: A Multidisciplinary Experiment for Undergraduate Students. J. Chem. Educ. 2018,95 (9), 1642-1647.View Article |
| [26] | Jorge G. Ibanez, J. G.; Puente-Caballero, R.; Torres-Perez, J.,; Bustos, D.; Carmona-Orbezo, A.; Sevilla, F.B. An Inexpensive Device for Studying Electrochromism. J. Chem. Educ. 2012,89 (9), 1205-1207.View Article |
| [27] | Schmidt, H-J.; Marohn A.; Harrison, A.G. Factors that prevent learning in Electrochemistry, J. Res. in Sci. Teaching, 2007, 44, 258-283.View Article |
| [28] | Garnet P.J.; Treagust, D.F. Conceptual difficulties experienced by senior high school students of electrochemistry: Electrochemical (galvanic) and electrolysis cells, J. Res. in Sci. Teach. 1992, 29, 1079-1099.View Article |
| [29] | Ogude, N.A.; Bradley, J.D. Electrode processes and aspects relating to cell EMF, current, and cell components in operating electrochemical cells. J. Chem. Educ. 1996, 73, 1145-1149.View Article |
| [30] | Huddle, A.H.; White, M.D.; Rodgers, F. Using a teaching model to correct known misconceptions in electrochemistry. J. Chem. Educ. 2000, 77, 104-110.View Article |
| [31] | Acar, B.; Tarhan, L. Effect of cooperative learning strategies on students’ understanding of concepts in electrochemistry. Int. J. Sci. and Math. Educ. 2007, 5, 349-373.View Article |
| [32] | Bard, A. J. (Ed.) Electrogenerated Chemi luminescence. Marcel Dekker, New York, 2004. |
| [33] | Richter, M.M. Electrochemi luminescence (ECL). Chem. Rev. 2004, 104, 3003-3036.View Article PubMed |
| [34] | Parveen, S.; Aslam, M.S.; Hu, L.; Xu, G. Electrogenerated Chemi luminescence. Protocols and Applications. Springer, Heidelberg, Germany, 2013. |
| [35] | Fähnrich, K.A.; Pravda, M.; Guilbault, G.G. Recent applications of electrogenerated chemiluminescence in chemical analysis. Talanta2001, 54, 531-559.View Article |
| [36] | Aristov, N; Habekost, A. Cyclic Voltammetry - A Versatile Electrochemical Method Investigating Electron Transfer Processes. World J. Chem. Educ. 2015, 3, 5 115-119. |
| [37] | Viswanathan, B.; Scibioh, M.A. Photoelectrochemistry. Principles and Practices, Alpha Science, Oxford, 2014. |
| [38] | Bard, A. J.; Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications, Wiley and Sons, New York, 2001. |
| [39] | Gosser, Jr, D. K. Cyclic Voltammetry. Simulation and Analysis of Reaction Mechanism, VCH, Weinheim, Germany, 1993. |
| [40] | Compton, R. G.; Banks, C. E. Understanding Voltammetry, 2nd Edition, Imperial College Press, 2011. |
| [41] | Mabbott, G. A. An Introduction to Cyclic Voltammetry, J. Chem. Educ. 1983, 60, 607-702.View Article |
| [42] | Kissinger, P. T.; Heineman, W. R. Cyclic Voltammetry, J. Chem. Educ. 1983, 60, 702-706.View Article |
| [43] | van Benschoten, J. J.; Lewis, Y. T.; Heineman, W. R.; Roston, D. A.; Kissinger, P. T. Cyclic Voltammetry Experiments, J. Chem. Educ. 1983, 60, 772-776.View Article |
| [44] | Amend, J.R.; Steward, G.; Kunzleman, T.S.; Collins, M.J. Affordable cyclic voltammetry, J. Chem. Educ. 2009, 86 (9), 1080-1081.View Article |
| [45] | Taleat Z.; Khoshroo, A.; Mazloum-Ardakani M. Screen-printed electrodes for biosensing: A review (2008-2013) MicrochimicaActa,2014,181, 865-891.View Article |
| [46] | Alberich, A.; Serrano, N.; Diaz-Cruz, J.M.; Arino, C.; Esteban, M. Substitution of mercury electrodes by bismuth-coated screen-printed electrodes in the determination of quinone in tonic water, J. Chem. Educ. 2013, 90, 1681-1684.View Article |
| [47] | DeAngelis, T. P.; Heineman, W. R. An Electrochemical Experiment Using an Optically Transparent Thin Layer Electrode, J. Chem. Educ. 1976, 53, 594 - 597.View Article |
| [48] | Hernandez, C. N.; Martin-Yerga, D.; Gonzalez-Garcia, M. B.; Hernandez-Santos, D.; Fanjul-Bolado, P. Evaluation of electrochemical, UV/VIS and Raman spectroelectrochemical detection of Naratripan with screen-printed electrodes, Talanta2018, 178, 85-88.View Article PubMed |
| [49] | Hernandez, C. N.; Gonzalez-Garcia, M. B.; Hernandez-Santos, D.; Heras, M. A.; Colina, A.; Fanjul-Bolado, P. Aqueous UV-VIS spectroelectrochemical study of the voltammetric reduction of graphene oxide on screen-printed carbon electrodes, Electro. Comm. 2016,64, 85-88.View Article |
| [50] | Kalyanasundaram, K. Photophysics, photochemistry and solar energy conversion with tris(bipyridyl)ruthenium (II) and its analogues, Coord. Chem. Rev.1982,46, 159-244.View Article |
