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Electrochemistry at nanoscale electrodes : individual single-walled carbon nanotubes (SWNTs) and SWNT-templated metal nanowires
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Dudin, Petr V., Snowden, Michael E., Macpherson, Julie V. and Unwin, Patrick R. (2011) Electrochemistry at nanoscale electrodes : individual single-walled carbon nanotubes (SWNTs) and SWNT-templated metal nanowires. ACS Nano, Volume 5 (Number 12). pp. 10017-10025. doi:10.1021/nn203823f ISSN 1936-0851.
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WRAP_Dudin, ACS Nano, 2011.pdf - Accepted Version Download (3161Kb) | Preview |
Official URL: http://dx.doi.org/10.1021/nn203823f
Abstract
Individual nanowires (NWs) and native single-walled carbon nanotubes (SWNTs) can be readily used as well-defined nanoscale electrodes (NSEs) for voltammetric analysis. Here, the simple photolithography-free fabrication of submillimeter long Au, Pt, and Pd NWs, with sub-100 nm heights, by templated electrodeposition onto ultralong flow-aligned SWNTs is demonstrated. Both individual Au NWs and SWNTs are employed as NSEs for electron-transfer (ET) kinetic quantification, using cyclic voltammetry (CV), in conjunction with a microcapillary-based electrochemical method. A small capillary with internal diameter in the range 30–70 μm, filled with solution containing a redox-active mediator (FcTMA+ ((trimethylammonium)methylferrocene), Fe(CN)64–, or hydrazine) is positioned above the NSE, so that the solution meniscus completes an electrochemical cell. A 3D finite-element model, faithfully reproducing the experimental geometry, is used to both analyze the experimental CVs and derive the rate of heterogeneous ET, using Butler–Volmer kinetics. For a 70 nm height Au NW, intrinsic rate constants, k0, up to ca. 1 cm s–1 can be resolved. Using the same experimental configuration the electrochemistry of individual SWNTs can also be accessed. For FcTMA+/2+ electrolysis the simulated ET kinetic parameters yield very fast ET kinetics (k0 > 2 ± 1 cm s–1). Some deviation between the experimental voltammetry and the idealized model is noted, suggesting that double-layer effects may influence ET at the nanoscale.
| Item Type: | Journal Article | ||||
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| Subjects: | Q Science > QD Chemistry T Technology > TA Engineering (General). Civil engineering (General) |
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| Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||
| Library of Congress Subject Headings (LCSH): | Nanowires, Nanotubes, Carbon, Electrochemistry, Nanostructured materials, Charge exchange, Electroplating | ||||
| Journal or Publication Title: | ACS Nano | ||||
| Publisher: | American Chemical Society | ||||
| ISSN: | 1936-0851 | ||||
| Official Date: | December 2011 | ||||
| Dates: |
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| Volume: | Volume 5 | ||||
| Number: | Number 12 | ||||
| Page Range: | pp. 10017-10025 | ||||
| DOI: | 10.1021/nn203823f | ||||
| Status: | Peer Reviewed | ||||
| Publication Status: | Published | ||||
| Access rights to Published version: | Restricted or Subscription Access | ||||
| Date of first compliant deposit: | 23 December 2015 | ||||
| Date of first compliant Open Access: | 23 December 2015 | ||||
| Funder: | European Research Council (ERC) | ||||
| Grant number: | ERC-2009-AdG 247143-QUANTIF (ERC) |
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