2010
DOI: 10.1021/jp908830d
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Electron Transfer Kinetics at Single-Walled Carbon Nanotube Electrodes using Scanning Electrochemical Microscopy

Abstract: An important open question on the electrochemistry of single-walled carbon nanotube (SWNT) electrodes concerns the sites at which electron transfer (ET) occurs. This issue is addressed herein for the case of a simple outer sphere redox couple, (ferrocenymethyl)trimethylammonium (FcTMA+). Using relatively sparse networks (<1% surface coverage) of electrically connected SWNTs, coupled to a scanning electrochemical microscopy (SECM) substrate generation−tip collection setup, we show that high rates of mass transp… Show more

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Cited by 57 publications
(62 citation statements)
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“…The modal value of the current distribution for the individual SWNTs with RuðNH 3 Þ 6 3þ∕2þ (Fig. 3A) (37,48).…”
Section: Resultsmentioning
confidence: 99%
See 1 more Smart Citation
“…The modal value of the current distribution for the individual SWNTs with RuðNH 3 Þ 6 3þ∕2þ (Fig. 3A) (37,48).…”
Section: Resultsmentioning
confidence: 99%
“…The use of an inert substrate avoids any possible EC contribution from the substrate. Two-dimensional networks of SWNTs are also of interest for at least two further reasons: (i) There is now ample evidence that such an electrode arrangement is optimal for maximizing signal to noise in voltammetric and amperometric measurements (26,37), and so understanding the intrinsic activity is valuable; and (ii) this arrangement presents a rather challenging array of closely spaced active elements for electrochemical imaging and highlights the capabilities of SECCM in resolving such complexity. More generally, we also show that the configuration of SECCM and an SWNT on an inert substrate leads to ultrahigh mass-transport rates that allow incredibly high HET rate constants to be quantitatively determined while also permitting distinction between different models of EC activity.…”
mentioning
confidence: 99%
“…In the opposite case, the consequences of increasing overlapping of the diffusion layers (26) will progressively decrease the nanoselectivity effects. ‡ Similar considerations would apply to other nanostructured electrode material, such as carbon nanotubes (27,28).…”
Section: Significancementioning
confidence: 95%
“…A significant advantage of SECM, particularly substrate voltammetry SECM which we consider herein, is the versatility to determine thermodynamic and kinetic properties at a plethora of electrode materials that would be difficult to fabricate into the TLC configuration such as graphene, 53 HOPG 28 and carbon nanotubes. 44 In this paper, we show how adsorption can greatly affect SECM voltammetric experiments, as well as highlighting how SECM can be used to reveal and quantify adsorption in electrochemical systems, building on earlier SECM adsorption studies in other situations. 19 The focus is ferrocenylmethyl trimethylammonium, FcTMA + , which undergoes an apparently simple one-electron oxidation, and has been used to study a wide range of electrode materials as an example of a fast outer-sphere redox couple.…”
mentioning
confidence: 89%