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Surface-sensitive spectro-electrochemistry using ultrafast 2D ATR IR spectroscopy


Lotti, Davide; Hamm, Peter; Kraack, Jan Philip (2016). Surface-sensitive spectro-electrochemistry using ultrafast 2D ATR IR spectroscopy. Journal of Physical Chemistry C, 120(5):2883-2892.

Abstract

A new method is presented for the combination of spectro-electrochemistry and femtosecond 2D IR spectroscopy. The key concept is based on ultrathin (similar to nm) conductive layers of noble metals and indium-tin oxide (ITO) as working electrodes on a single-reflection attenuated total reflectance (ATR) element in conjunction with ultrafast, multidimensional ATR spectroscopy. The ATR geometry offers prominent benefits in ultrafast spectro-electrochemistry, that is, surface sensitivity for studying electrochemical processes directly at the solvent-electrode interface as well as the application of strongly IR-absorbing solvents such as water due to a very short effective path length of the evanescent wave at the interface. We present a balanced comparison between usable electrode materials regarding their performance in the ultrafast ATR setup. The electrochemical performance is demonstrated by vibrational Stark-shift spectroscopy of carbon monoxide (CO) adsorbed to platinum-coated, ultrathin ITO electrodes. We furthermore measure vibrational relaxation and spectral diffusion of the stretching mode from surface-bound CO dependent on the applied potential to the working electrode and find a negligible impact of the electrode potential on ultrafast CO dynamics.

Abstract

A new method is presented for the combination of spectro-electrochemistry and femtosecond 2D IR spectroscopy. The key concept is based on ultrathin (similar to nm) conductive layers of noble metals and indium-tin oxide (ITO) as working electrodes on a single-reflection attenuated total reflectance (ATR) element in conjunction with ultrafast, multidimensional ATR spectroscopy. The ATR geometry offers prominent benefits in ultrafast spectro-electrochemistry, that is, surface sensitivity for studying electrochemical processes directly at the solvent-electrode interface as well as the application of strongly IR-absorbing solvents such as water due to a very short effective path length of the evanescent wave at the interface. We present a balanced comparison between usable electrode materials regarding their performance in the ultrafast ATR setup. The electrochemical performance is demonstrated by vibrational Stark-shift spectroscopy of carbon monoxide (CO) adsorbed to platinum-coated, ultrathin ITO electrodes. We furthermore measure vibrational relaxation and spectral diffusion of the stretching mode from surface-bound CO dependent on the applied potential to the working electrode and find a negligible impact of the electrode potential on ultrafast CO dynamics.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
08 University Research Priority Programs > Solar Light to Chemical Energy Conversion
Dewey Decimal Classification:540 Chemistry
Language:English
Date:11 February 2016
Deposited On:23 Jan 2017 13:58
Last Modified:08 Dec 2017 22:30
Publisher:American Chemical Society (ACS)
ISSN:1932-7447
Funders:Swiss National Science Foundation, University Research Priority Program (URPP) for solar light to chemical energy conversion (LightChEC), Center of Microscopy and Imaging at the University of Zurich (ZMB)
Publisher DOI:https://doi.org/10.1021/acs.jpcc.6b00395

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