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Studies of Electrified Interfaces using Vibrational Sum Frequency Generation

Wallentine, Spencer K
http://orcid.org/0000-0001-5539-018X
http://rave.ohiolink.edu/etdc/view?acc_num=osu1618593424214523

Abstract Details

2021, Doctor of Philosophy, Ohio State University, Chemistry.
Herein I describe Vibrational Sum Frequency Generation, a non-linear spectroscopy with vibrational specificity and high sensitivity for buried interfaces. I describe work to extend Vibration Sum Frequency Generation to electrochemical interfaces using Surface Plasmon Resonance. Using this method, I can detect molecules across the vibrational region at current densities greater than 1 mA/cm2 and with detection limits as low as 1% of a monolayer. During carbon dioxide reduction on gold electrodes I observe atop CO, a surface intermediate. Using Stark spectroscopy of the CO intermediate I measure the potential dependent interfacial electric field. I also prescribe a way to account for dipole-dipole and third order contributions to the SFG signal and comment on potential dependent intensity and coverage changes. Correlations between Stark field measurements and the SFG Intensity reveal potential dependent changes to the double layer structure that favor carbon dioxide reduction. I find that cite blocking by electrolyte cations lowers the steady state coverage of CO, but that its presence increases carbon dioxide reduction activity. Stark spectroscopy of several cations reveals that the increase in activity is not related to the magnitude of the interfacial electric field but is instead related to specific interactions of the hydrated cations with intermediates. Preliminary measurements of interfacial water also show differences between cations, which may corroborate these findings.
Robert Baker (Advisor)
Heather Allen (Committee Chair)
James Coe (Committee Member)
142 p.
Chemistry
Sum Frequency Generation; Electrocatalysis; Vibrational Stark Effect; Carbon Dioxide Reduction; Electrochemistry; Infrared Spectroscopy; Electric Fields; Electrochemical Double Layer; Alkali Cations

Recommended Citations

Citations

  • Wallentine, S. K. (2021). Studies of Electrified Interfaces using Vibrational Sum Frequency Generation [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1618593424214523

    APA Style (7th edition)

  • Wallentine, Spencer. Studies of Electrified Interfaces using Vibrational Sum Frequency Generation. 2021. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1618593424214523.

    MLA Style (8th edition)

  • Wallentine, Spencer. "Studies of Electrified Interfaces using Vibrational Sum Frequency Generation." Doctoral dissertation, Ohio State University, 2021. http://rave.ohiolink.edu/etdc/view?acc_num=osu1618593424214523

    Chicago Manual of Style (17th edition)

osu1618593424214523
168
© 2021, some rights reserved.Creative Commons License Studies of Electrified Interfaces using Vibrational Sum Frequency Generation by Spencer K Wallentine is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License. Based on a work at etd.ohiolink.edu.
This open access ETD is published by The Ohio State University and OhioLINK.
Release 3.2.12