Snowden, Michael E., Güell, Aleix G., Lai, Stanley Chi Shing, McKelvey, Kim M. (Kim Martin), Ebejer, Neil, O’Connell, Michael A., Colburn, Alex W. and Unwin, Patrick R.. (2012) Scanning electrochemical cell microscopy : theory and experiment for quantitative high resolution spatially-resolved voltammetry and simultaneous ion-conductance measurements. Analytical Chemistry, Volume 84 (Number 5). pp. 2483-2491. ISSN 0003-2700

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Abstract

Scanning electrochemical cell microscopy (SECCM) is a high resolution electrochemical scanning probe technique that employs a dual-barrel theta pipet probe containing electrolyte solution and quasi-reference counter electrodes (QRCE) in each barrel. A thin layer of electrolyte protruding from the tip of the pipet ensures that a gentle meniscus contact is made with a substrate surface, which defines the active surface area of an electrochemical cell. The substrate can be an electrical conductor, semiconductor, or insulator. The main focus here is on the general case where the substrate is a working electrode, and both ion-conductance measurements between the QRCEs in the two barrels and voltammetric/amperometric measurements at the substrate can be made simultaneously. In usual practice, a small perpendicular oscillation of the probe with respect to the substrate is employed, so that an alternating conductance current (ac) develops, due to the change in the dimensions of the electrolyte contact (and hence resistance), as well as the direct conductance current (dc). It is shown that the dc current can be predicted for a fixed probe by solving the Nernst-Planck equation and that the ac response can also be derived from this response. Both responses are shown to agree well with experiment. It is found that the pipet geometry plays an important role in controlling the dc conductance current and that this is easily measured by microscopy. A key feature of SECCM is that mass transport to the substrate surface is by diffusion and, for charged analytes, ion migration which can be controlled and varied quantifiably via the bias between the two QRCEs. For a working electrode substrate this means that charged redox-active analytes can be transported to the electrode/solution interface in a well-defined and controllable manner and that relatively fast heterogeneous electron transfer kinetics can be studied. The factors controlling the voltammetric response are determined by both simulation and experiment. Experiments demonstrate the realization of simultaneous quantitative voltammetric and ion conductance measurements and also identify a general rule of thumb that the surface contacted by electrolyte is of the order of the pipet probe dimensions.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Faculty of Science > Chemistry Faculty of Science > Molecular Organisation and Assembly in Cells (MOAC)
Library of Congress Subject Headings (LCSH):	Electrochemistry, High resolution electron microscopy, Electron microscopy, Chemical kinetics, Electrochemical analysis, Voltammetry, Conductometric analysis, Chemistry, Analytic -- Quantitative
Journal or Publication Title:	Analytical Chemistry
Publisher:	American Chemical Society
ISSN:	0003-2700
Date:	6 March 2012
Volume:	Volume 84
Number:	Number 5
Page Range:	pp. 2483-2491
Identification Number:	10.1021/ac203195h
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Funder:	European Research Council (ERC), European Regional Development Fund (ERDF), Seventh Framework Programme (European Commission) (FP7/2007-2013), Advantage West Midlands (AWM), Marie Curie Intra-European Fellowship (IEF), Engineering and Physical Sciences Research Council (EPSRC), University of Warwick. Molecular Organisation and Assembly in Cells, National Physical Laboratory (Great Britain)
Grant number:	ERC-2009-AdG 247143-QUANTIF, IEF (236885, 275450)
References:	1 Ebejer, N.; Schnippering, M.; Colburn, A.W.; Edwards, M.A.; Unwin, P.R. Anal. Chem. 2010, 82, 9141 2 Lai, S. C. S.; Dudin, P. V.; Macpherson, J. V.; Unwin, P. R. J. Am. Chem. Soc., 2011, 133, 10744 3 Bard, A. J.; Mirkin, M. V. Scanning Electrochemical Microscopy; Marcel Dekker: New York, 2001 4 Amemiya, S.; Bard, A. J.; Fan, F.-R. F.; Mirkin, M. V.; Unwin, P. R. Annu.Rev. Anal. Chem. 2008, 1, 5 (a) Bard, A. J.; Fan, F. R. F.; Kwak, J.; Lev, O. Anal. Chem. 1989, 61, 132 (b) Kwak, J.; Bard, A. J. Anal. Chem. 1989, 61, 1221 (c) Bard, A. J.; Fan, F.-R. F.; Pierce, D. T.; Unwin, P. R.; Wipf, D. O.; Zhou, F. Science, 1991, 254, 68 6 (a) Macpherson, J. V.; Unwin, P. R. Anal. Chem. 2000, 72, 276 (b) Kranz, C.; Friedbacher, G.; Mizaikoff, B. Anal. Chem. 2001, 73. 2491 (c) Macpherson, J. V.; Unwin, P. R. Anal. Chem. 2001, 73, 550 (d) Macpherson, J. V.; Unwin, P. R.; Hillier, A. C.; Bard, A. J. J. Am. Chem. Soc. 1996, 118, 6445 (e) Kueng, A.; Kranz, C.; Lugstein, A.; Bertagnolli, E.; Mizaikoff, B. Angew. Chem. Int. Edit. 2003, 42, 3238 (f) Kueng, A.; Kranz, C.; Lugstein, A.; Bertagnolli, E.; Mizaikoff, B. Angew. Chem. Int. Edit. 2005, 44. 3419 7 (a) Hengstenberg, A.; Kranz, C.; Schuhmann, W. Chem. Eur. J. 2000, 6, 1547 (b) Lee, Y.; Ding, Z. F.; Bard, A. J. Anal. Chem. 2002, 74, 3634 (c) Buchler, M.; Kelley, S. C.; Smyrl, W. H. Electrochem. Solid St. 2000, 3, 35 (d) Takahashi, Y.; Shiku, H.; Murata, T.; Yasukawa, T.; Matsue, T. Anal. Chem. 2009, 81, 9674. 8 (a) Katemann, B. B.; Schulte, A.; Calvo, E. J.; Koudelka-Hep, M.; Schuhmann, W. Electrochem. Comm. 2002, 4, 134 (b) Katemann, B.B.; Inchauspe, C. G.; Castro, P. A.; Schulte, A.; Calvo, E. J.; Schuhmann, W. Electrochim. Acta 2003, 48, 1115 (c) Horrocks, B.R.; Schmidtke, D.; Heller, A. Bard, A.J. Anal. Chem. 1993, 65, 3605. (d) Alpuche-Aviles, M.A.; Wipf, D.O. Anal. Chem. 2001, 73, 4873 (e) Baranski, A. S.; Diakowski, P. M. J. Solid State Electr. 2004, 8, 683 (f) Ervin, E. N.; White, H. S.; Baker, L. A. Anal. Chem. 2005, 77, 5564 (g) Ervin, E. N.; White, H. S.; Baker, L. A.; Martin, C. R. Anal. Chem. 2006, 78, 6535. (h) Kurulugama, R. T.; Wipf, D. O.; Takacs, S. A.; Pongmayteegul, S.; Garris, P. A.; Baur, J. E. Anal. Chem. 2005, 77. 1111 (i) Diakowski, P.M.; Ding, Z. Phys. Chem. Chem. Phys. 2007, 9. 5966 9 (a) McKelvey, K.; Edwards, M. A.; Unwin, P. R. Anal. Chem., 2010, 82 (15), 6334 (b) McKelvey, K.; Snowden, M. E.; Peruffo, M.; Unwin, P. R. Anal. Chem. 2011, 83, 6447 (c) Takahashi, Y.; Shevchuk, A. I.; Novak, P.; Zhang, Y.; Ebejer, N.; Macpherson, J. V.; Unwin, P. R.; Pollard, A. J.; Roy, D.; Clifford, C. A.; Shiku, H.; Matsue, T.; Klenerman, D.; Korchev, Y. E. Angew. Chem. Int. Edit. 2011, 50, 9638 10 (a) Takahashi, Y.; Shevchuk, A. I.; Novak, P.; Murakami, Y.; Shiku, H.; Korchev, Y. E.; Matsue, T. J. Am. Chem. Soc. 2010, 132, 10118 (b) Comstock, D. J.; Elam, J. W.; Pellin, M. J.; Hersam, M. C. Anal. Chem. 2010, 82, 1270 (c) Takahashi, Y.; Shevchuk, A. I.; Novak, P.; Zhang, Y.; Ebejer, N.; Macpherson, J. V.; Unwin, P. R.; Pollard, A. J.; Roy, D.; Clifford, C. A.; Shiku, H.; Matsue, T.; Klenerman, D.; Korchev, Y. E. Angew. Chem. Int. Edit. 2011, 50, 9638 11 (a) Momotenko, D.; Cortes-Salazar, F.; Lesch, A.; Wittstock, G.; Girault, H.H. Anal. Chem. 2011, 83. 5275 (b) Lohrengel, M.M.; Moehring, A.; Pilaski, M. Electrochim. Acta 2001, 47, 137 (c) Hassel, A.W.; Lohrengel, M.M.; Electrochim. Acta 1997, 42, 3327 (d) Spaine, T.W.; Baur, J.E. Anal. Chem. 2001, 73. 930 12 (a) Williams, C.G.; Edwards, M.A.; Colley, A.L.; Macpherson, J.V.; Unwin, P.R. Anal. Chem. 2009, 81, 2486 (b) Yang, D.; Han, L.; Yang, Y.; Zhao, L.-B.; Zong, C.; Huang, Y.-F.; Zhan, D.; Tian, Z.-Q. Angew. Chem. Int. Edit. 2011, 50. 8679. 13 (a) Suter, T.; Bohni, H. Electrochim. Acta 1997, 42, 3275 (b) Suter, T.; Bohni, H. Electrochim. Acta 1998, 43, 2843 14 (a) Rodolfa, K. T.; Bruckbauer, A.; Zhou, D. J.; Korchev, Y. E.; Klenerman, D. Angew. Chem. Int. Edit. 2005, 44, 6854 (b) Shevchuk, A. I.; Gorelik, J.; Harding, S. E.; Lab, M. J.; Klenerman, D.; Korchev, Y. E. Biophys. J. 2001, 81, 1759 (c) Shevchuik, A. I.; Frolenkov, G. I.; Sanchez, D.; James, P. S.; Freedman, N.; Lab, M. J.; Jones, R.; Klenerman, D.; Korchev, Y. E. Angew. Chem. Int. Edit. 2006, 45, 2212 15 (a) Laslau, C.; Williams, D. E.; Wright, B. E.; Travas-Sejdic, J. J. Am. Chem. Soc. 2011, 133, 5748 (b) Chen, C.-C.; Zhou, Y.; Baker, L. A. ACS Nano 2011, 5, 8404 (c) Chen, C.-C.; Derylo, M. A.; Baker, L. A. Anal. Chem. 2009, 81, 4742 16 Wei, C.; Bard, A. J.; Nagy, G.; Toth, K. Anal. Chem. 1995, 67, 1346 17 Shao, Y.; Mirkin, M.V. Anal. Chem. 1998, 70, 3155 18 Szentirmay, M. N.; Martin, C. R.; Anal. Chem. 1984, 56, 1898 19 Bartle, K. D.; Myers, P. J. Chromatogr. A 2001, 916, 3 20 (a) White, H.S.; Bund, A. Langmuir 2008, 24, 12062 (b) Wang, G.L.; Zhang, B.; Wayment, J.R.; Harris, J.M.; White, H.S. J. Am. Chem. Soc. 2006, 128, 7679 21 Lide, R. CRC Handbook of Chemistry and Physics, CRC Press, USA, 2001 22 Bertoncello, P.; Ciani, I.; Li, F.; Unwin, P.R. Langmuir, 2006, 22, 10380 23 Newman, J.S.; Thomas-Alyea, K.E. Electrochemical Systems, Wiley-Interscience, 2004, p271-295 24 Bard, A. J.; Faulkner, L. R. Electrochemical Methods 2nd ed.; John Wiley and Sons: New York, 2001. 25 Rodolfa, K.T.; Bruckbauer, A.; Zhou, D. J.; Schevchuk, A.I.; Korchev, Y.E.; Klenerman, D. Nano Lett 2006, 6, 252 26 Heinze, J. J. Electroanal. Chem. 1981, 124, 73 27 Edwards, M. A.; Williams, C. G.; Whitworth, A. L.; Unwin, P. R. Anal. Chem. 2009, 81, 4482 28 (a) Dumitrescu, I.; Dudin, P. V.; Edgeworth, J. P.; Macpherson, J. V.; Unwin, P. R. J. Phys. Chem. C 2010, 114, 2633 (b) Dumitrescu, I.; Unwin, P. R.; Wilson, N. R.; Macpherson, J. V. Anal. Chem. 2008, 80, 3598
URI:	http://wrap.warwick.ac.uk/id/eprint/44776

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