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04/26/2012

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2009, 81, 130–138

Cyclic Voltammograms at Coplanar and Shallow Recessed Microdisk Electrode Arrays: Guidelines for Design and Experiment

Jidong Guo and Erno Lindner* ¨ Department of Biomedical Engineering, University of Memphis, 330 Engineering Technology, Memphis, Tennessee 38152 Although microdisk electrode arrays (MEAs) have been extensively used for more than three decades, the existing rules do not provide an unambiguous formula for the calculation of the minimum interelectrode distance (d) necessary for steady-state current response. With the aim of formulating generally applicable guidelines for design and experiment with MEAs, cyclic voltammograms were simulated for coplanar and shallow recessed microdisk electrode arrays with various interelectrode distances and dimensionless scan rates (V). The dimensionless scan rate (V) is a function of the radius (a) of the individual electrodes in the array, the diffusion coefﬁcient (D) of the analyte, and the potential scan rate (v). The cyclic voltammograms at microdisk electrode arrays are grouped into ﬁve categories corresponding to the contributions of linear and radial diffusion to the overall responses. These categories are illustrated in a zone diagram based on the effect of V and d on the shape of cyclic voltammograms. The zone diagram reveals the minimum d and a cluster of linked d and V values that are incident to sigmoidal wave responses. For shallow recessed microdisk electrode arrays, the zones representing hemispherical diffusion are larger than that for coplanar arrays. The minimum d necessary for hemispherical diffusion becomes smaller as recess depth increases. With the zone diagram, one can predict the type of the cyclic voltammograms that can be expected for different microelectrode array geometries and experimental conditions. The ﬁtting between simulation and experimental data validates our conclusions.

Similar to individual microelectrodes, microdisk electrode arrays have a high faradic to capacitive current ratio.1 The magnitude of their amperometric responses is similar to macroelectrodes. Microelectrode arrays (MEAs) have shown their advantages in a variety of electroanalytical applications, e.g., endcolumn detection in electrophoresis,2,3 clinical chemistry,4,5 and

* To whom correspondence should be addressed. E-mail: elindner@ memphis.edu. Phone: 901-678-5641. Fax: 901-678-5281. (1) Amatore, C. In Physical Electrochemistry: Principles, Methods and Applications; Rubenstein, I., Ed.; Marcel Dekker: New York, 1995; p 131. (2) Liu, J.; Zhou, W. H.; You, T. Y.; Li, F. L.; Wang, E. K.; Dong, S. J. Anal. Chem. 1996, 68, 3350–3353. (3) Kappes, T.; Hauser, P. C. Electroanalysis 2000, 12, 165–170.

environmental monitoring.6-8 Since their introduction,9 microelectrode arrays became well-accepted tools in electrophysiology10,11 with high spatial and temporal resolution for cell and tissue studies. MEA-like behaviors are widely recognized on nanoparticles and carbon nanotube modiﬁed surfaces,12-14 highly ordered pyrolytic graphite15 and other graphite electrodes,16,17 borondoped diamond electrodes,18 and electrodes modiﬁed with electrochemically inert membranes.19,20 All these structures with MEA-like behavior can be considered as partially blocked electrodes21-23 or electrochemically heterogeneous electrodes.24 Microdisk electrode arrays could serve as simpliﬁed models of the real systems.

(4) Zhang, S. Q.; Zhao, H. J.; John, R. Anal. Chim. Acta 2000, 421, 175–187. (5) Albers, J.; Grunwald, T.; Nebling, E.; Piechotta, G.; Hintsche, R. Anal. Bioanal. Chem. 2003, 377, 521–527. (6) Belmont, C.; Tercier, M. L.; Bufﬂe, J.; Fiaccabrino, G. C.; Koudelka-Hep, M. Anal. Chim. Acta 1996, 329, 203–214. (7) Feeney, R.; Kounaves, S. P. Anal. Chem. 2000, 72, 2222–2228. (8) Feeney, R.; Kounaves, S. P. Electroanalysis 2000, 12, 677–684. (9) Thomas, D. A.; Springer, P. A.; Loeb, G. E.; Berwald-Netter, Y.; Okun, L. M. Exp. Cell Res. 1972, 74, 61–66. (10) Maher, M. P.; Pine, J.; Wright, J.; Tai, Y. C. J. Neurosci. Methods 1999, 87, 45–56. (11) Stett, A.; Egert, U.; Guenther, E.; Hofmann, F.; Meyer, T.; Nisch, W.; Haemmerle, H. Anal. Bioanal. Chem. 2003, 377, 486–495. (12) Dai, X.; Wildgoose, G. G.; Salter, C.; Crossley, A.; Compton, R. G. Anal. Chem. 2006, 78, 6102–6108. (13) Welch, C. W.; Compton, R. G. Anal. Bioanal. Chem. 2006, 384, 601–619. (14) Wilson, N. R.; Guille, M.; Dumitrescu, I.; Fernandez, V. R.; Rudd, N. C.; Williams, C. G.; Unwin, P. R.; Macpherson, J. V. Anal. Chem. 2006, 78, 7006–7015. (15) Banks, C. E.; Davies, T. J.; Wildgoose, G. G.; Compton, R. G. Chem. Commun. 2005, 7, 829–841. (16) Davies, T. J.; Moore, R. R.; Banks, C. E.; Compton, R. G. J. Electroanal. Chem. 2004, 574, 123–152. (17) Davies, T. J.; Hyde, M. E.; Compton, R. G. Angew. Chem., Int. Ed. 2005, 44, 5121. (18) Holt, K. B.; Bard, A. J.; Show, Y.; Swain, G. M. J. Phys. Chem. B 2004, 108, 15117–15127. (19) Sabatani, E.; Rubinstein, I. J. Phys. Chem. 1987, 91, 6663–6669. (20) Jeoung, E.; Galow, T. H.; Schotter, J.; Bal, M.; Ursache, A.; Tuominen, M. T.; Stafford, C. M.; Russell, T. P.; Rotello, V. M. Langmuir 2001, 17, 6396– 6398. (21) Amatore, C.; Saveant, J. M.; Tessier, D. J. Electroanal. Chem. 1983, 147, ´ 39–51. (22) Brooks, B. A.; Davies, T. J.; Fisher, A. C.; Evans, R. G.; Wilkins, S. J.; Yunus, K.; Wadhawan, J. D.; Compton, R. G. J. Phys. Chem. B. 2003, 107, 1616– 1627. (23) Davies, T. J.; Brooks, B. A.; Fisher, A. C.; Yunus, K.; Wilkins, S. J.; Greene, P. R.; Wadhawan, J. D.; Compton, R. G. J. Phys. Chem. B. 2003, 107, 6431– 6444. (24) Davies, T. J.; Bank, s C. E.; Compton, R. G. J. Solid State Electrochem. 2005, 9, 797–808. 10.1021/ac801592j CCC: $40.75 2009 American Chemical Society Published on Web 11/20/2008

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Analytical Chemistry, Vol. 81, No. 1, January 1, 2009

Electrochim. H. H. 79. 217–222. Electroanalysis 1998. 587. J.As a powerful electroanalytical method.31 In other words. 2000. M.. G. Ferrigno.35 the three-dimensional simulation is unappealing if a two-dimensional approximation can provide satisfactory results. Electroanal. 486. and v. S. steady-state responses are expected if the hemispherical diffusion layers of the individual microelectrodes are not perturbed by the diffusion layers of the neighboring microelectrodes. a. Chem. where the repeating unit is illustrated by the mesh-ﬁlled triangle. respectively. H. (35) Beriet. H. Glidle.. 4377–4388. G. 5717–5725. Compton. and D. 1978. Rev. J. 39. which reveals the necessary d for sigmoidal response. 138–145. Polarogr. Koudelka-Hep.34 To show the consequences of this MEA geometry compared to coplanar MEAs. the selection of an optimal microelectrode density in an array is important. Horne. Although commercially available ﬁnite element softwares have been used to solve similar three-dimensional problems. The approach of Davies and Compton is essentially different from the previous efforts because it considers several experimental parameters in determining the required minimum d for steady-state voltammetric response. However. Although Davies and Compton pointed out that a generally applicable formula to predict d should contain all factors inﬂuencing the mass transport. J. Chem. In the absence of a comprehensive formula.33 In this paper. 177–187..21 reveals that regardless of the size of d there will be cross talk between adjacent (25) Saito. 2009 131 . the design guidelines for microdisk arrays should rather provide a necessary d that is large enough to allow the development of hemispherical diffusion layers over the individual microelectrodes in the array in a window of potential scan rates. Chem. January 1. Cooper. 585. Girault. Y. if the center-to-center distance (d) between two adjacent microelectrodes in an array is too small or too large. THEORY Model for a Coplanar Inﬁnite Microdisk Electrode Array in Hexagonal Lattice. H. P. J. The difﬁculty in formulating a universal expression for d can be reduced by using dimensionless parameters.. J. T. A hexagonally arranged microdisk array is shown in Figure 1a. (28) Fletcher. J. D. Acta 1994.29. Chem. 254–262. 1968. (26) Lee. Electroanal. G. A microdisk electrode array is claimed to have steady-state response25 if d > 12a (1) individual microelectrodes at certain scan rates because the diffusion layer at disk electrodes continuously enlarges with the square root of time. G. (30) Sandison. 1. Electroanal. 89. Anal.. 502.e. its power to simplify this particular problem and the possibility of utilizing it for formulating general guidelines for the design and experiments was overlooked. Obviously. F.. 63–82. (27) Davies.. Tokuda. where n is the number of electrons transferred in the electrode reaction. K. (29) Seddon... The simulation of the voltammetric response of a coplanar microdisk array is a three-dimensional problem. Matsuda. Chem.. T. This fabrication process generally provides MEAs that are slightly recessed. Consequently.. J. C. M. A. in a quiescent solution.. Jiang. v. B. F is the Faraday constant. 247– 260. C. the cyclic voltametric behavior of shallow recessed microdisk electrode arrays was simulated and the necessary d for sigmoidal response was determined. Amemiya. 2002.. R. The twodimensional simulation is indeed a widely accepted ap(31) Amatore. i. H. 2001. 56–64. Electroanal. Girault. 74. C. G. this long-standing view was proven not satisfactory by Girault.. J. In cyclic voltammetric studies with microdisk electrode arrays.. once the adjacent diffusion layers overlap. Fosset. But the zone diagram of Amatore et al. the microdisk electrode array will lose its unique features and becomes similar to a macroelectrode or an individual microelectrode. no sufﬁciently large d exists that could prevent the overlap of the diffusion layers over the individual microelectrodes in the array at all possible potential scan rates. J. a is not considered in eq 3..26. Anal. MEAs are most commonly fabricated with photolithographic techniques. Girault. 15. 2006.26 Later. 10. S. Consequently. Y. To overcome the lack of generally acceptable design criteria. 2005. 502–512. E. General guidelines for designing microdisk electrode arrays could avoid lengthy and expensive experimental optimization. peak-shaped CVs with smaller current densities are observed. a. (36) Gueshi. M. N. Ferrigno. J.28 The absence of theory-based general guidelines for microelectrode array design impelled experimental optimization attempts. Commun. Shao. Jones.. The phenomenon of overlapping diffusion layers is commonly termed as “cross talk” or shielding effect.22. Anal. (32) Rodgers. Chem. (34) Fiaccabrino.32 nF va2 4RT D where a is the radius of an individual electrode in the array. Compton. J. R. L. The diffusion layer evolving over a microdisk electrode array in cyclic voltammetric experiments depends on d. Vol. 2377– 2386. and D. R is the universal gas constant. Analytical Chemistry. B. 81. cyclic voltammetry is often the ﬁrst choice to characterize a new electrochemical system. the dimensionless scan rate V instead of three independent parameters a. Anicet. Davies and Compton formulated a function to calculate d ∆E v d>2 2D (3) where ∆E is the potential range from the foot of the forward wave to the reverse point and v is the potential scan rate.30 Most previous theoretical studies focused on ﬁnding a d value that is sufﬁciently large to exclude the possibility of diffusion layer overlapping. Although a similar dimensionless scan rate has been used in theoretical studies of cyclic voltammetry at MEA. However. R. H. 2007.. Chem. 1999. Chem. the effect of V and d on the shape of CVs recorded with coplanar microelectrode arrays is presented in a zone diagram.. Beriet. 9276–9285.. most importantly. T. and T is the thermodynamic temperature. C.. v. 1. 1996. D. Davies and Compton27 found that the much more stringent design criterion of Fletcher and Horne28 d g 20a (2) V) (4) is also insufﬁcient. Electrochem. M. H. simulations might be used for the accurate determination of the minimum d in a microelectrode array. 68. (33) Chevallier. R. Electroanal. No.

(E . t) ∂r ∂cR(r. t) ) DR + + ∂t r ∂r ∂r2 ∂z2 [ [ ] (8) ] (9) where the cO.5 is taken in this work). 2009 . t) (12) DO DO ∂cO(r.E0 ) RT ) (7) where k0 is the standard heterogeneous rate constant for the redox couple. z. z. z. DO. z. Szabo. January 1. z. t) 1 ∂cO(r. a fast oneelectron-transfer reaction with Bulter-Volmer kinetics is considered O + e.28. z. 81. t) ∂r ∂cR(r. The net ﬂuxes passing through the boundaries of hexagons are zero in voltammetric experiments. 160.l < z < zmax (19) (20) r)a ) 0 -l < z < 0 132 Analytical Chemistry. 0 e z e zmax Figure 1. z. t) ∂z ] ] ] z)-l ) -DR [ ∂cR(r. t) ∂r ∂cO(r. 0 e r e R0. The initial conditions for coplanar and recessed microelectrode arrays are given as cO ) cb. z. Vol. The diffusion of species O and R in the solution can be expressed as ∂cO(r. t) ∂z ] z)0 ) kfcO(r. r)a ) DR [ [ ∂cR(r. t) ∂r ] ] r)0 )0 . z. z. z. 0 < r < R0 cR ) 0. 0 e z e zmax proach. z. only the species O is present in the solution with initial bulk concentration of cb. then cR = cb .21. t) ∂2cO(r. Chem. each microelectrode can be assigned its own hexagon as shown in Figure 1a. z. z. The cylindrical symmetry of this unit cell simpliﬁes the simulation to a two-dimensional problem in which only the plane shown in the left panel of Figure 1b needs to be considered. (10) (11) cR ) 0. No. which is far from the outer boundary of the diffusion layer. 1. t) 1 ∂cR(r. the boundary conditions are DO (5) [ [ [ ∂cO(r. z. 0 e r e R0. t) ∂2cR(r. t) ∂2cO(r. The accuracy of the twodimensional simulation compared to three-dimensional simulation can be found in the Supporting Information.R)F (E . and DR are the concentrations and diffusion coefﬁcients of respective species. The same idea can also be applied to recessed microdisk electrode arrays with a recess depth l (Figure 1b. t) ∂z ] z)-l ) kfcO(r. z. z.37 which is especially attractive when a large number of simulations must be performed. z. t) kbcR(r. (a) Microdisk array with hexagonal arrangement.36. z.E0 ) RT ( ) DO (6) DO ∂cO(r. A. t) ∂r r)0 ) DR (37) Shoup. D. are deﬁned by RF kf ) k0 exp . t) ∂2cR(r. (b) space domains deﬁned for a ﬁnite element simulation of cyclic voltammetry at coplanar (left) and recessed (right) regular microdisk electrode arrays. t) ∂r ∂cO(r. shown in the right panel of Figure 1b. z ) zmax. t) ∂z ] ] ] r)0 ) 0 0 < z < zmax ) 0 0 < z < zmax (13) r)R0 (14) z)0 ) 0 a < r < R0 (15) (16) (17) cO ) cb. Before the experiment starts. zmax is the maximum z value in the simulation domain. like the mesh-ﬁlled circle in Figure 1a. J. right panel) To simulate the cyclic voltammetric response. t) ∂r ∂cO(r. E0′ is the formal potential. t) ∂r ∂cR(r. R is the transfer coefﬁcient (R ) 0. t) ) DO + + ∂t r ∂r ∂r2 ∂z2 ∂cR(r. t) ∂z r)0 ) DR r)R0 ) DR DO z)0 ) DR [ [ [ ∂cR(r. z. z. z. 19–26. z ) zmax. t) (18) The forward and backward rate constants.cO applies to the entire simulation domain.h R kb kf where R0 ) d[31/2/(2π)]1/2. z. t) kbcR(r. insulator is in white. These hexagons are replaced by equal-area circles with radius R0. If we take the common assumption of DO ) DR. z. z.. t) ∂z ] ] ] ] z)0 ) -DR [ ∂cR(r. and E is the applied potential on the electrode/solution interface. cR.kb ) k0 exp - ( (1 . The boundary conditions for a coplanar microdisk electrode array (Figure 1b left panel) are DO [ [ [ [ ∂cO(r. Hexagonal mirodisk electrode array and the conditions for the diffusion domain approach. z. 0 < r < R0 For a recessed microdisk electrode array. kf and kb. In brief. Electroanal. 1984. The two-dimensional simulation takes some assumptions.

z. January 1. The diffusion over the MEA can be classiﬁed as ﬁve categories. The time-dependent diffusion problems deﬁned above were solved by a Comsol Multiphysics version 3. Categories I and II were not distinguished before. 2009 133 . 4 GB memory. diffusion mode of partial overlapping of adjacent diffusion layers.0 . The simulations have been performed at a variety of dimensionless scan rates (V) at selected d values ranging between d = 2.0.2 (Comsol. transition between planar and hemispherical diffusion layers. Simulation of each CV took between 5 and 10 min on a PC equipped with a Pentium D 3. diffusion mode of complete overlaping of individual diffusion layers. and Windows XP Professional Edition operating system. (III) hemispherical diffusion layers on individual microdisk. Deﬁnition of Dimensionless Transition Scan Rates criterion transition scan rates V12 V23 V34 V45 Imax.Ei) sin-1 sin π 2(Er . t) ∂z ] z)-l dr (24) for recessed microdisk electrode arrays. single Imax. For a general treatment. reverse/Imax. which applies the ﬁnite element method. Table 1. The second scale bar represents a relative concentration scale for the contour lines. has been described in eq 4. the following dimensionless parameters were used: CO ) cO ⁄ cb CR ) cR ⁄ cb R)r⁄a Z)z⁄a L)l⁄a k0a K0 ) D ε) τ) nFE RT 4Dt a2 (25) (26) (27) (28) (29) (30) (31) (32) Figure 2. With these simulations.31 The dimensionless scan rate.05 < Imax. MA) program. single Imax. z. To have a quantitative deﬁnition of these categories. individual Imax. diffusion mode between planar and hemispherical diffusion. single Imax. (II) mixed diffusion layers on individual microdisk. (IV) mixed diffusion layers. individual > Iss. (IV) mixed diffusion layer due to overlapping of the individual diffusion layers.0 < Iss. (III) hemispherical diffusion layers over the individual microelectrodes. These categories are shown schematically in Figure 2: (I) planar diffusion layer over the individual microelectrodes. 81.Er) v (21) where Ei is the initial potential and Er is the reversal potential in cyclic voltammetry.31 γ ) γlinear . single for d g 3.05 for d g 23.γsingle ) 0. No. the borders between the diffusion categories could be formulated as dimensionless transition scan rates using the criteria formulated Analytical Chemistry. 1. These simulations were also aimed to provide generally applicable guidelines for MEA design (d.05 ) 0. V. individual < Iss..and eqs 14-17 also apply. forward (γ) γ γ γ γ ) γlinear . Simulated concentration proﬁles with isoconcentration contour lines over a microelectrode array representing the ﬁve main categories of diffusion modes: (I) planar diffusion layers on individual microdisk. The time scale (tc) of the cyclic voltammetric experiment is tc ) 2(Ei . simulations have been performed to reveal the correlation between d and V and to determine the dominating mode of diffusion in cyclic voltammetric experiments with MEAs under different experimental conditions (v. t) ∂z ] z)0 dr (23) for coplanar microdisk electrode arrays and i ) 2πFDO ∫ a 0 r [ ∂cO(r. a) and experiment (v.05 for d < 23. i..4 GHz processor. D). The triangle wave of E-t in cyclic voltammetry can be expressed as πvt 2 E ) Ei + (Er .3a and d ) 200a. (V) planar diffusion layer over the entire microelectrode array. Zone Diagram of Cyclic Voltammetry at Coplanar Microelectrode Array.e. Inc. Burlington. Typical CVs of the each category are shown at the right. single for d < 3. single Imax. Imax. (V) planar diffusion layer over the entire microelectrode array. the red color represents the bulk concentration and the blue color represents zero concentration.0. individual < Imax.Ei) { [ ]} 0 e t e tc (22) The current passing through the individual microelectrode/ solution interfaces can be calculated by i ) 2πFDO ∫ a 0 r [ ∂cO(r. Vol.05 ) 0. individual > Iss. individual individual Imax. In the scale bar next to the ﬁgure. D). (II) mixed diffusion layers over individual microelectrodes.

it should be noted that there is no real “steady state” at a microdisk electrode array in a quiescent solution.. a) and the applied experimental conditions (v.0a as a universally applicable necessary center-to-center distance (dnecessary) in coplanar microdisk electrode array design that is required for recording sigmoidal voltammetric responses. Anal. N. are fully planar diffusion dominated with no overlap of the diffusion layers of the individual electrodes in an array.g. D) correspond to the criteria of zone III. the CVs grouped into zone I. Martin. Yang. given D ) 10-5 cm2/s.08562. reverse to Imax.73 exp(-log d/1. 1998. V12. (41) Baker. related to their partial linear and partial radial diffusion. C. Zones IV and VI are virtually separated by the extension of the V23 borderline. Zone II is bordered by the V12.e. i. V23. 1995. and the V34 lines.3a and d ) 200a there is no such a centerto-center distance at which all V is incident to steady-state voltammograms. 10041–10046.07 and V = 0. M. Crooks. 102. Koudelka-Hep. Chem. and V45 border lines divide the V versus d diagram into zones labeled with roman numbers. Indeed the CVs of MEAs with d ) 24a can fall in all of the zones depending on the applied V.0617) + 15. the area above the V12 line. II and III. Finding the points on line (38) Arrigan.Figure 3. M. d ) 24a.341 × 10-6.41 CVs grouped into category IV in Figure 2. Expressions of Zone Borderlines in Figure 3 zone borderlines V12 V23 logV34a logV45a a expressions 136.384 V/s or a ) 100 nm and v ) 0. and IV and V.. (40) Zoski.11 Equations ﬁtted to simulated points.096 V/s. in which both V and d are plotted on logarithmic scales (Figure 3). Berdondini. V12. R. P. 2007... The V12. Zones I-V represent the diffusion categories of Figure 2. forward) values of a CV to a criterion given in Table 1. even if they were manufactured with extremely large center-to-center distances between individual electrodes. M. It is deﬁned as the area in between V23 and V34 lines. The results of these simulations also provided a V versus d plot. Similarly. respectively as shown in Figure 2.02 or 0. The CVs in this zone are in a mixed diffusion mode with contribution from linear and radial diffusion. Even the CV recorded with an array with interelectrode distance of 200a can show notable deviation from sigmoidal wave once the dimensionless scan rate is below 9. The “standard” CVs were deﬁned as ones solely linear diffusion controlled (V ) 7789 at a single inlaid microdisk electrode) or solely hemispherical diffusion controlled (V ) 10-6 at a single inlaid microdisk electrode). Table 2.38-40 and in selecting the most adequate experimental conditions in their applications. 81. for example. This intersection deﬁnes d ) 23. The shape deviation was assessed by comparing γ (γ ) Imax. C. V23. from the zone diagram it is obvious that the selection of a slightly larger value than the dnecessary..05 V/s) can easily fall into zone IV (partial linear and partial radial diffusion mode). Chem.8 exp(-log d/0. Zone diagram of cyclic voltammetric behavior at microelectrode arrays. the CVs of nanoelectrode arrays recorded at commonly applied scan rates (e. CVs in zone V correspond to category V behavior in Figure 2 where a planar diffusion layer spreads over the entire surface of an electrode array. V34. The symbols and acronyms used to deﬁne the borderlines in the zone diagram are included in the list of symbols (Table 3). Consequently. No. P. (39) Menon. and V45 represent the borderlines between the diffusion modes I and II. were deﬁned as the boundaries between categories I-V. zone II in Figure 3 corresponds to category II in Figure 2. V23. a zone diagram. These dimensionless transition scan rates. 1. W. Vol. January 1.3 0. V. L.. Zone III has unique importance because sigmoidal voltammetric responses can only be achieved in cyclic voltammetric experi134 Analytical Chemistry. V = 0. V34.94) .13. D. To achieve sigmoidal response requires the careful selection of a combination of a and v values (with given D) to make the dimensionless scan rate fall in the narrow gap between the V34 and V23 lines at d ) 24a. i. where γlinear is the ratio of Imax. J.. forward in a fully linear diffusion-controlled CV. The intersection of the V23 and V34 borderlines of zone III is at d ) 23. . 79. V23. These boundaries were quantiﬁed with current criteria and a subjectively selected level of deviation (5%) from the shape of “standard” CVs. III and IV (II and IV in certain domain). is not sufﬁcient for a steady-state response.19. 67. He. 0. V is the dimensionless scan rate (eq 4). Zone III in Figure 3 corresponds to category III in Figure 2.87) .g.. It is essential to recognize that between d ) 2. The expressions for the borderlines between different diffusion categories are listed in Table 2. However. respectively.. Anal. 1474–1484. This dimensionless scan rate can be generated. Phys. The information provided by this diagram is expected to be useful in designing nanoelectrode arrays and nanoelectrode ensembles. 2009 ments with MEAs if their design (d.57 475.08562 26. Analyst 2004.e. 129. can fall into zones IV and VI in Figure 3. reverse/Imax. The borderlines of Figure 3.. For this reason. W. R. G. Chem. in Table 1. For example. e. 1920–1928. by the combination of a ) 50 nm and v ) 0. and V45. S. and θ is the fraction of electrochemically active area in the array. 1157–1165. V34.0a. d is the center-to center distance of individual electrodes in the array (measured in units of a). Note that in this zone the CVs of the individual microelectrodes in an array are same as the CVs of a single microelectrode. indicating that the dense packed arrays leave no possibility for sigmoidal voltammetric response because the overlapping of diffusion layers occurs in shorter time then needed for achieving hemispherical diffusion layer.12 exp(-log d/3.

its signiﬁcance can be generalized for other types of microelectrode arrays or microelectrode ensembles by changing the x-axis from the center-tocenter distance (d) to the fractional area of the microelectrodes in an array (θ).16a. Chem. forwarda Imax. individual) less than the steady-state current on a single disk (Iss. single) and shapes that are 5% different from the ideal sigmoidal shape. singlea Imax. 3599–3604. Lines V12 and V45 intersect at d ) 2. 2009 135 . forward.. Although the zone diagram of Figure 3 is based on the simulations reﬂecting the geometrical conditions of hexagonally arranged microdisk electrode arrays. eventual patterns on an electrode surface will not inﬂuence the CVs. deﬁned as the potential difference from the foot of the forward wave to the reverse point in a cyclic voltammogram Faraday constant current passing through the individual microelectrode/ solution interfaces (eqs 23 and 24) steady-state current in the CV obtained on a single microdisk electrode maximum current in the CV obtained on a single microdisk electrode maximum current for the forward reaction in a CV (e. S. The simpler current and shape comparisons for the lower part of V34 are possible because all CVs with V e V23 are sigmoidal waves at a single electrode. reversea Imax. characterizing the contribution of cottrellian diffusion in a CV γ value calculated from a fully linear diffusion-controlled CV γ value calculated from a CV obtained on a single microdisk electrode with certain V dimensionless potential (eq 31) potential scan rate dimensionless time (eq 32) fraction of active area in a microelectrode array D DO and DR E Ei Er E0′ ∆E F i Iss. the points on the section of the V45 line above the V23 line were determined by ﬁnding dimensionless scan rates that would generate CVs for the individual disks with lower maximum current than could be expected for a single electrode and with 5% smaller γ compared with a fully planar diffusion dominated CV.e.. With d smaller than 2. Anal. W. reverse/Imax. i. This pair-by-pair comparison with single-electrode CVs was necessary because above the V23 line the shapes of the CVs contain both linear and radial diffusion components. singlea Imax. The criteria for the maximum current quantify the diffusion layer overlapping while the criteria for γ measure the tolerance of deviation. 74. the line V34 separates two kinds of CV behaviors at microelectrode arrays with 5% tolerance: (1) the individual disks in an array behave like independent microelectrodes when a particular V and d combination places the CV above the V34 line. maximum anodic current) maximum current in the CV obtained on an individual microdisk electrode in a MEA heterogeneous rate constant for reduction as deﬁned in eq 6 heterogeneous rate constant for oxidation as deﬁned in eq 7 standard heterogeneous rate constant for the redox couple dimensionless rate constant (eq 30) recess depth dimensionless recess depth (eq 29) number of electrons transferred in the electrode reaction oxidized species in the solution cylindrical coordinate reduced species in the solution dimensionless r coordinate (eq 27) universal gas constant radius of a circle equal in area to the individual microelectrode hexagon (Figure 1a) time time scale of the cyclic voltammetric experiment (eq 21) thermodynamic temperature dimensionless scan rate (eq 4) dimensionless transition scan rate borderline between diffusion categories I and II in the zone diagram (Figure 3) dimensionless transition scan rate borderline between diffusion categories II and III in the zone diagram (Figure 3) dimensionless transition scan rate borderline between the diffusion categories III and IV (II and IV in certain domain) in the zone diagram (Figure 3) dimensionless transition scan rate borderline between diffusion categories IV and V in the zone diagram (Figure 3) cylindrical coordinate maximum z value in the simulation domain dimensionless z coordinate (eq 28) transfer coefﬁcient γ ) Imax. represent CVs with maximum currents on individual disks (Imax. E. January 1.. above line V23. which can be peak-shaped CVs and sigmoidal CVs.. Symbols and Acronyms symbol a cO and cR cb CO CR d dnecessary deﬁnition radius of the individual electrodes in the array concentration of the oxidized and reduced species in the solution bulk solution concentration dimensionless concentration of the oxidized species (eq 25) dimensionless concentration of the reduced species (eq 26) center-to-center distance between two adjacent microelectrodes in an array. indicating a patterned surface with electrochemically active (electrode) and inactive (insulated) areas. single) and with 5% increased γ compared to the value expected for a single electrode at the same V (γsingle). If an inﬁnite microdisk electrode array is packed with microelectrode sites denser than this limit. Vol. once d becomes larger than 2.Table 3. 2002. In summary. For the hexagonal arrangement of electrodes in an MEA θ becomes 2πa2 √3d2 θ) (33) a Currents are normalized by the steady-state current on a single microdisk electrode. i. maximum cathodic current) maximum current for the reverse reaction in a CV (e. Some graphite electrodes30 and nanoparticles42 or carbon nanotube modiﬁed electrodes may drop into this special category. 81. which is large enough to make it possible to record a sigmoidal wave on a MEA dnecessary is measured in units of a diffusion coefﬁcient diffusion coefﬁcients of the oxidized and reduced species in the solution applied potential on the electrode/solution interface initial potential in cyclic voltammetry reversal potential in cyclic voltammetry formal potential potential range in eq 3. were determined by ﬁnding dimensionless scan rates that would generate CVs with lower maximum current on individual disks than could be expected for a single electrode (Imax.g. to the ratio of the active (electrode) versus inactive (insulator) areas in a MEA. the CVs recorded with such arrays will be always fully planar diffusion dominated at any v and a combination in a quiescent solution. The points on the section of the V34 line. (2) the current responses of the individual microelectrodes in an array are inﬂuenced by signiﬁcant overlapping of the individual diffusion layers when a selected V and d combination places the CVs below the V34 line. However. the microelectrode array will always behave as a macroelectrode with an electrochemically homogeneous surface.16a.. Analytical Chemistry. No. individuala kf kb k0 K0 l L n O r R R R R0 t tc T V V12 V23 V34 V45 z zmax Z R γ γlinear γsingle ε v τ θ V34 and line V45 above line V23 is less trivial.e. the shapes of MEA CVs will change with the dimensionless scan rate. Wang. below the V23 line. The points on line V34. Similar to the above. 1. Dong. d is measured in units of a center-to-center distance of two adjacent individual microelectrodes.g.16a. (42) Cheng..

Consequently. Indeed. the area of zone III for recessed-well MEAs is larger compared to coplanar microdisk electrode arrays. Electroanal. the intersection of the V23 and V34 lines determines dnecessary.43 Similarly.The zone diagram simpliﬁes to a line diagram of V if it is applied to single microelectrodes. 2. the decrease is controlled by the shift in the V34 position. For L < 0. and (III) solely hemispherical diffusion controlled. and 5. Dubuque. we extended our study to shallow recessed microdisk electrode arrays. The V34 and V45 lines have no relevance for single microelectrodes. As shown in Figure 5. But zone II and the V23 line are actually very important in the determination of the necessary d for attaining sigmoidal voltammetric response with a MEA. Other chemicals were reagent grade and were used as received from commercial sources. Slanted lines represent V34 lines. But for L > 0. respectively. IV. 2. 1. Figure 4. the intersections labeled for the different L values are V23/V34 line intersections. or for predicting the shape of voltammograms of MEAs or single microelectrodes if the geometrical parameters and the experimental conditions are known.218 exp - ( L + 0. it is impossible to formulate an eloquent answer for dnecessary. 81. With the help of these V12 and V23 points. for 0 < L e 2. and VI and the line V23 were not included in the zone diagram of Amatore et al. the location of the V23 line has fundamental importance in the determination of dnecessary. Horizontal lines represent V23 lines.492 ) The upper and lower limits of the dimensionless scan rate providing sigmoidal CVs with shallow recessed microdisk electrode arrays with given d and L can be determined from the V23 and V34 lines corresponding to the given recess depth (L). All aqueous solutions were prepared with 18. J. Indeed. A conservative estimate for the lower limit of the dimensionless scan rate can be obtained with the help of the V34 line for coplanar MEAs. and D as the following: (I) planar diffusion controlled. J. Necessary Interelectrode Distance (dnecessary) for Shallow Recessed Microdisk Electrode Arrays. the V34 line descends as L increases. Microdisk electrode arrays fabricated by thin-ﬁlm photolithography are normally shallow recessed. which deﬁne the dnecessary values for L ) 0.75 values. Lindner.75. reﬂecting the increased diffusion times in the well. Chem.2. the modes of mass transport in cyclic voltammetric experiments can be quantitatively categorized for any given v. in the range of 0 e L e 5. Louis. dnecessary ) 10.86 + 6. the zone diagram has been devised with this intent by employing the dimensionless scan rate and interelectrode distance. On the other hand.. Without unambiguous dimensionless transition scan rates separating the mixed diffusion zones (zones II and IV) and the hemispherical diffusion zone (zone III). Ferrocenemethanol (97%) was obtained from Sigma-Aldrich (St. a. and 5 (numbers labeling the cross sections). 0. Submitted. the position of the V34 line changes with changing L. II. Based on Amatore’s zone diagram. But CVs belonging in zones I. The hexagonally arranged gold microdisk arrays were fabricated by Aegis 136 Analytical Chemistry. 0. Interestingly. was ﬁtted to an exponential decay function for the convenience of application for shallow recessed microdisk electrode array. It has been demonstrated that the V versus d zone diagram is adequate for selecting a combination of microdisk electrode array design and experimental parameters for a desired behavior in cyclic voltammetric experiments. and V. These categories are reﬂected in the shape of the single-microelectrode CVs. No.34 To provide accurate zone diagram for this class of MEAs.085 62). dnecessary gradually decreases as L increases (Figure 5). 0. the value of V23 is larger than the value of V23 at L ) 0 (0. Since the motivation for the zone diagram presented in this work has been to provide convenient guidelines for MEA design and for selecting adequate experimental conditions in experiments with MEAs.2. Enlarged section of the zone diagram (Figure 3) showing the V23 and V34 line cross sections for shallow recessed microdisk electrode arrays with L ) 0. this decrease is a consequence of the shifts in V23 and V34 lines. dnecessary (measured in units of a) as function of the dimensionless recess depth (L) for shallow recessed microdisk electrode arrays. IA) Electrodes and Electrochemical Measurments.435 exp - ( L + 0. E.75. As emphasized above.75. Barnstead. January 1. as L changes from 0 to 30.2 MΩ · cm-1 resistivity deionized water (Nanopure. The position of the V23 line changes simultaneously with changes in the recess depth (L).0888 (34) 0. Figure 5. MO).222 ) 9.21 one can predict the shapes of the CVs that belong in zones III. as shown in Figure 4. In Figure 4. V23 passes a maximum at L ) ∼0. 0. EXPERIMENTAL SECTION Chemicals. (II) mixed linear and radial diffusion controlled. 2009 . due to the oppositely changing trends of V23 and V34 lines in this recess depth range. versus L.0888 + 0. This line is separated into three segments by points corresponding to the V12 and V23 lines in the zone diagram.75. The plot of dnecessary (43) Guo. Vol.

J. The γ values for the simulated CV of coplanar arrays exceed the 5% limit. RESULTS AND DISCUSSION Fitting with Experimental Results at Recessed Microdisk Electrode Arrays. d ) 150 µm (a). but as shown in Figure 6b. with d = 30a and l ) 0. and this is consistent with what we observed at a single shallow recessed microdisk electrode.05 V/s.035 V/s with the same a and D) from Figure 4. a Ag/AgCl reference electrode (CH Instruments.43 The value of γ in the CV of coplanar MEA slightly exceeds the 5% tolerance. TX). Our experiments at MEA with d ) 20a and L ) 0. d ) 100 µm. In the three-electrode setup.84. d ) 20a (b. These results show that the experimental value of V34 for recessed microelectrode arrays. As shown in Figure 6c. l ) 1 µm. Vol. The value of V34 for d ) 30a and L ) 0. the dnecessary for a recessed microdisk electrode array with L ) 0. TX) and a Pt wire counter electrode were used in combination with one of the Pt microelectrodes or a microelectrode array as working electrode. 77. Comparison of the experimentally recorded CVs at shallow recessed microdisk electrode arrays with simulation results at coplanar and recessed arrays. Apparently. The γ values for the computed and experimental CVs of Figure 6b were almost exactly at the 5% deviation line. January 1. l = 0. With increasing overlapping of the diffusion layers. and D ) 7. Experimental data obtained at microelectrode arrays with a ) 5 µm. The dnecessary for coplanar microdisk electrode array is 23. the simulated CV for d ) 30a. The individual gold disk electrodes of a ) 5 µm and l ) 1 µm were patterned with d ) 100 or 150 µm interelectrode distances over a 3-mm-diameter circular area using polyimide as insulating material. (Huntsville.006 574). With a scan rate of 0.065 74 (b).4 × 10-6 cm2/s for ferrocenemethanol44 shows excellent agreement on both the forward and reverse scans with experimental data obtained with an array of a ) 5 µm. while the value of V34 for a coplanar array with d ) 30a is 0. the effect of overlapping diffusion layers becomes apparent on the CVs at (44) Guo.02 V/s (V ) 0.1 M NaNO3 solution were background-subtracted. 2005.023 35.. the recessed electrode geometry obstructs the expansion of the diffusion layer toward to the wall of the diffusion domain and delays the overlapping of the adjacent diffusion layers. a practically sigmoidal wave was observed at the recessed microelectrode array with a ) 5 µm. labeled as a dotted horizontal line in Figure 6a. and 0.2 from Figure 4 is determined as 0. No. 2009 137 .2 is 17. 1. c). is lower than 0. Figure 6. Dotted horizontal lines (dark yellow) in panels a and b indicate 5% increase of γ from baseline.016 44 (a) 0. and l ) 1 µm at v ) 0. S. The comparison of the simulated curves of the coplanar and the recessed MEAs shows that the linear diffusion contribution is somewhat larger at the coplanar microelectrode array. Figure 5 predicts that dnecessary is smaller on a recessed microdisk electrode array compared with a coplanar array. These interconnected microelectrode arrays8.016 44 (v ) 0. Austin.05 V/s and a ) 5 µm with D ) 7. From Figure 5. Chem.2a.2 support this expectation. Anal. and l ) 0. Amemiya. The simulated curve for a recessed array is also in almost perfect agreement with the experimental CV (Figure 6b). the difference in the shape of the CVs of the recessed and the coplanar microelectrode arrays becomes more signiﬁcant (Figure 6c).2a. Austin.2 V/s. d ) 150 µm. Cyclic voltammetric experiments were performed with a CHI 760C electrochemical workstation (CH Instruments. Inc.0 µm (Figure 6a).34 are made by patterning hexagonally arranged circular openings by standard photolithography into a 1-µm-thick polyimide insulation layer over a large gold disk electrode. while the value of γ in the CV of recessed MEA is less than 5%. and l = 1.2a for recessed. It is important to emphasize that the simulations in this account were performed for microelectrode arrays of inﬁnite extension. the same recessed MEAs. Experimental CVs in Figure 6a belong in zone III. 2147–2156. AL) on glass substrate using standard thin-ﬁlm photolithography. It means that the somewhat different contribution of microelecAnalytical Chemistry.006 574 (c) at arrays with d ) 30a (a).Technologies Group. The individual microdisk electrodes in the MEAs used in our experiments are formed on the bottom of slightly recessed wells with 1-µm depth.0. 81. Simulations presented with corresponding dimensionless scan rates of 0.4 × 10-6 cm2/s for ferrocenemethanol in Figure 6a).011 67 (v ) 0. at a scan rate of 0. c) in 1 mM ferrocenemethanol and 0. and d ) 100 µm (b.

when the dimension of the array drops in the microelectrode range. in zone IV close to the V34 borderline. 81.44 the diffusion layers over the entire array will be hemispherical for zone V. 2008...g. their contribution to the total current is independent from their location in the array. the interference related to the limited size of an array is negligible when the CVs are categorized as categories I. These categories are illustrated in a zone diagram based on the effect of the dimensionless scan rate (V) and the center-to-center distance between electrodes (d) on the shape of cyclic voltammograms. 2009 .e. i. one can also predict the voltammetric behavior of microdisk electrode array if the design parameters of the array and the experimental conditions are known. 1. especially for densely packed arrays. the difference between inﬁnite and ﬁnite arrays is not negligible. The intersection of two borderlines between mixed diffusion and hemispherical diffusion provides the necessary d that is required for sigmoidal wave in cyclic voltammetric experiments. The behavior of MEAs in cyclic voltammetric experiments has been grouped into ﬁve main categories in a quantitative way based on the contribution of linear and radial diffusion to the overall current responses. It shows that coplanar MEAs of d g 23a are expected to present a sigmoidal wave only if the experimental scan rate falls into a certain scan rate range. This material is available free of charge via the Internet at http://pubs. The zone diagram provides a generally applicable. However. No. This makes the consideration of a ﬁnite MEA size (the edge effect) in simulations rather complicated. Received for review July 29. microelectrodes close to the edge of the array also present higher currents and less linear diffusion contribution in comparison to the central microelectrodes. Using the zone diagram. and III (Figure 2) because in these categories the individual microelectrodes in the arrays behave like single microelectrodes. Three-dimensional simulations (data not shown) demonstrate that if considerable overlapping of the diffusion layers inﬂuences the MEA responses.org. CONCLUSIONS Cyclic voltammograms of coplanar and recessed microdisk electrode arrays have been simulated to categorize their voltammetric behavior. Vol. e. ACKNOWLEDGMENT The authors thank the ﬁnancial support of the NIH/NHLBI #1 RO1 HL079147 grant. But in zone IV besides the area close to line V34. dnecessary were determined for 0 < L < 5. As a special case of ﬁnite microdisk arrays. Accepted October 27. The boundaries between the zones were revealed by numeric simulations and validated by experimental data. 2008..g. AC801592J 138 Analytical Chemistry.acs. unambiguous guideline for microelectrode array design. and in zones V and VI.trodes located at the edge of the array to the total current has not been considered. nanoelectrode arrays in micrometer size. e. For recessed microdisk electrode arrays. The effect of the different current responses of microelectrodes at the edge of the array is also insigniﬁcant when the overlapping of the diffusion layers between the individual microelectrodes in the array is not very severe. II. then besides the microelectrodes at the very edge26 of the array. The area of the zone in which sigmoidal CVs can be expected is larger for shallow recessed arrays in the zone diagram. January 1. SUPPORTING INFORMATION AVAILABLE Additional information as noted in text.40.

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