Observing Single, Heterogeneous, One-Electron Transfer Reactions

Stephanie Zaleski; M. Fernanda Cardinal; Jordan M. Klingsporn; Richard P. Van Duyne

doi:10.1021/acs.jpcc.5b10652

Observing Single, Heterogeneous, One-Electron Transfer Reactions

Stephanie Zaleski, M. Fernanda Cardinal, Jordan M. Klingsporn, Richard P. Van Duyne^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

39 Scopus citations

Abstract

Understanding electrochemical events on the single-molecule level is crucial for fields such as catalysis and biological systems. A variety of techniques exist to study the electrochemistry of single molecules, but few provide correlated chemical information. Herein, we study the electrochemistry of rhodamine 6G in nonaqueous conditions and demonstrate the first statistic electrochemical single-molecule SERS (EC-SMSERS) proof of single-electron transfer events. We find that the distribution of reduction events is broader than that in a bulk electrochemical experiment. The distribution of the reduction potentials can be explained by molecular reorientation and variations of the local surface site or chemical potential of the Ag nanoparticle. Our results contribute toward understanding electrochemical behavior of single molecules on the nanoscale monitored by SERS and the ultimate goal of controlling single-electron transfer processes.

Original language	English (US)
Pages (from-to)	28226-28234
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	119
Issue number	50
DOIs	https://doi.org/10.1021/acs.jpcc.5b10652
State	Published - Nov 23 2015

Funding

This work was supported by Air Force Office of Scientific Research MURI (Grant FA9550-14-1-0003) and the National Science Foundation (MRSEC Grants NSF DMR-1121262 and NSF CHE-1152547). This work made use of the EPIC facility (NUANCE Center - Northwestern University), which has received support from the MRSEC program (Grant NSF DMR-1121262) at the Materials Research Center; the Nanoscale Science and Engineering Center (Grant NSF EEC-0647560) at the International Institute for Nanotechnology; and the State of Illinois, through the International Institute for Nanotechnology. M.F.C. acknowledges the access to the solvent system of the Stoddart group at Northwestern University for the provided dried acetonitrile.

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
General Energy
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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10.1021/acs.jpcc.5b10652

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abstract = "Understanding electrochemical events on the single-molecule level is crucial for fields such as catalysis and biological systems. A variety of techniques exist to study the electrochemistry of single molecules, but few provide correlated chemical information. Herein, we study the electrochemistry of rhodamine 6G in nonaqueous conditions and demonstrate the first statistic electrochemical single-molecule SERS (EC-SMSERS) proof of single-electron transfer events. We find that the distribution of reduction events is broader than that in a bulk electrochemical experiment. The distribution of the reduction potentials can be explained by molecular reorientation and variations of the local surface site or chemical potential of the Ag nanoparticle. Our results contribute toward understanding electrochemical behavior of single molecules on the nanoscale monitored by SERS and the ultimate goal of controlling single-electron transfer processes.",

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N2 - Understanding electrochemical events on the single-molecule level is crucial for fields such as catalysis and biological systems. A variety of techniques exist to study the electrochemistry of single molecules, but few provide correlated chemical information. Herein, we study the electrochemistry of rhodamine 6G in nonaqueous conditions and demonstrate the first statistic electrochemical single-molecule SERS (EC-SMSERS) proof of single-electron transfer events. We find that the distribution of reduction events is broader than that in a bulk electrochemical experiment. The distribution of the reduction potentials can be explained by molecular reorientation and variations of the local surface site or chemical potential of the Ag nanoparticle. Our results contribute toward understanding electrochemical behavior of single molecules on the nanoscale monitored by SERS and the ultimate goal of controlling single-electron transfer processes.

AB - Understanding electrochemical events on the single-molecule level is crucial for fields such as catalysis and biological systems. A variety of techniques exist to study the electrochemistry of single molecules, but few provide correlated chemical information. Herein, we study the electrochemistry of rhodamine 6G in nonaqueous conditions and demonstrate the first statistic electrochemical single-molecule SERS (EC-SMSERS) proof of single-electron transfer events. We find that the distribution of reduction events is broader than that in a bulk electrochemical experiment. The distribution of the reduction potentials can be explained by molecular reorientation and variations of the local surface site or chemical potential of the Ag nanoparticle. Our results contribute toward understanding electrochemical behavior of single molecules on the nanoscale monitored by SERS and the ultimate goal of controlling single-electron transfer processes.

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Observing Single, Heterogeneous, One-Electron Transfer Reactions

Abstract

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