Scanning electrochemical microscopy:  theory and application of the transient (chronoamperometric) SECM response

Bard, Allen J.; Denuault, Guy; Friesner, Richard A.; Dornblaser, Bright; Tuckerman, Laurette S.

doi:10.1021/ac00013a019

Cited by 109 publications

(81 citation statements)

References 17 publications

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“…Considering the microelectrode and diffusion coefficient first, Bard et al have shown by simulation that a microelectrode will reach a normalized current of 2.249 after a dimensionless time, τ, of 0.1 following a potential step. 35 The dimensionless time is related directly to the diffusion coefficient of the species employed and with an inverse square relationship to the radius of the microelectrode (e.g. τ ) Dt/a 2 , where D, t, and a represent the diffusion coefficient of the redox species employed, the real time, and the radius of the microelectrode, respectively).…”

Section: Resultsmentioning

confidence: 99%

Electrochemical and Photographic Detection of Cavitation Phenomena within a Variable Frequency Acoustic Field

1998

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Electrochemical measurements of localized mass transfer effects within a cavitating liquid (sound field, 20-100 kHz) are reported. The contribution of acoustic streaming to mass transfer recorded at a microelectrode (Pt, 10 µm diameter) is shown to be negligible in comparison to transient events. Active zones, within which high event density was observed, are shown to exist within the liquid. Transient events were recorded, within these active zones, at a frequency as high as ca. 4500/s, which was deemed the limit of resolution of the microelectrode and sort routine employed rather than a cavitation effect. These active zones are shown to be dynamic in nature. Average mass transfer coefficients within these active transient event zones of the order of 0.3 cm s -1 are reported as well as the influence of acoustic pressure on mass transfer within these active zones. Photographic evidence indicates the volume and dynamic nature of the active cavitation zones within the cell.

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Section: Resultsmentioning

confidence: 99%

Electrochemical and Photographic Detection of Cavitation Phenomena within a Variable Frequency Acoustic Field

1998

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“…Generation-collection modes of SECM are especially useful for studying homogeneous reactions [23]. Chronoamperometric SECM, in which i T is recorded as a function of time, is particularly useful for studying mass transport effects [24]. In alternating current (AC) mode SECM, an AC signal is superimposed onto the potentiostat input signal, which generates an alternating current signal that depends on L and the substrate properties [25].…”

Section: Principles Of Scanning Electrochemical Microscopymentioning

confidence: 99%

Ultramicroelectrode Voltammetry and Scanning Electrochemical Microscopy in Room Temperature Ionic Liquids

Walsh

2015

Electrochemistry in Ionic Liquids

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This year (2014) marks the 25th anniversary of the invention of SECM in the Bard lab at the University of Texas [1,2]. Such is the impact of its development that the scanning electrochemical microscope (SECM-the same abbreviation is used for the instrument and the method) is now a "textbook" electroanalytical tool used in a wide variety of applications, ranging from fundamental studies of mass and charge transfer dynamics to molecular transport across biological cell membranes, corrosion analysis and electrocatalyst screening [3,4]. Given the increasing popularity of room-temperature ionic liquids (RTILs) in electrochemical studies and devices [5,6], it was perhaps inevitable that SECM measurements would also be carried out in RTILs and a number of such studies have appeared in the recent literature [7][8][9][10]. However, the unique physicochemical properties of RTILs can lead to very unusual behaviour being observed during SECM. For example, drastic differences in the rates of diffusion of charged and uncharged species can arise in RTILs and such phenomena have been studied using SECM [11]. The high viscosities of RTILs also mean that unusual SECM responses are often obtained in RTILs, unless one carefully controls the experimental parameters [9].In this chapter, those studies that have involved performing SECM in RTILs will be discussed. As we will see, a relatively small number of such studies have been carried out to date, but unique electrochemical insights have been obtained. In attempting to fully describe how the properties of RTILs affect SECM in these media, the voltammetric behaviour of UMEs must also be described as the operation of the SECM depends on the behaviour of UMEs during electrolytic reactions. The chapter begins with a brief description of the principles of UME voltammetry and

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“…Bard and co-workers, the pioneers of this technique, were quite aware of this problem and in their very first papers, one can already find a rather large number of papers dealing with numerical simulations of SECM experiments. [6][7][8][9] Since then, one can still find a lot of papers dealing with numerical simulations. The aim of this review is not to gather all of them.…”

Section: Introductionmentioning

confidence: 99%

Analytical Expressions for Quantitative Scanning Electrochemical Microscopy (SECM)

2010

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Scanning electrochemical microscopy (SECM), is a recent analytical technique in electrochemistry, which was developed in the 1990s and uses microelectrodes to probe various surfaces. Even with the well-known disc microelectrodes, the system geometry is not as simple as in regular electrochemistry. As a consequence even the simplest experiments, the so-called positive and negative feedback approach curves, cannot be described with exact analytical expressions. This review gathers all the analytical expressions available in the SECM literature in steady-state feedback experiments. Some of them are claimed as general expressions, other are presented as approximate. Their validity is discussed in the light of the current understanding and computer facilities.

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Scanning electrochemical microscopy: theory and application of the transient (chronoamperometric) SECM response

Cited by 109 publications

References 17 publications

Electrochemical and Photographic Detection of Cavitation Phenomena within a Variable Frequency Acoustic Field

Electrochemical and Photographic Detection of Cavitation Phenomena within a Variable Frequency Acoustic Field

Ultramicroelectrode Voltammetry and Scanning Electrochemical Microscopy in Room Temperature Ionic Liquids

Analytical Expressions for Quantitative Scanning Electrochemical Microscopy (SECM)

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