University of Illinois Urbana-Champaign

Electrochemical and spectroelectrochemical investigations of interfacial electrode processes

Hatfield, Kendrich O'Donaghue

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HATFIELD-DISSERTATION-2022.pdf

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https://hdl.handle.net/2142/115644

Description

Title
Electrochemical and spectroelectrochemical investigations of interfacial electrode processes
Author(s)
Hatfield, Kendrich O'Donaghue
Issue Date
2022-04-21
Director of Research (if dissertation) or Advisor (if thesis)
Rodríguez-López, Joaquín
Doctoral Committee Chair(s)
Rodríguez-López, Joaquín
Committee Member(s)
  • Murphy, Catherine
  • Jain, Prashant K
  • Han, Hee-Sun
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
  • Electrochemistry
  • Surface-enhanced Raman spectroscopy
  • Scanning Electrochemical Microscopy
  • Thin film electrodes
Abstract
Electrode interfaces are critical players in the development of medical, industrial, and energy-related technologies and a thorough understanding of the surface electrochemistry is required to design better devices and materials. Analytical methods for studying electrode surfaces in situ vary widely and give information ranging from chemical speciation to electron transfer properties. Electrochemical methods using the analyte of interest as the working electrode provide vital interfacial properties such as kinetics, mass transport, and thermodynamics of electrode processes across the entire interface. In this dissertation, such techniques are shown to determine the charge transport properties and mechanisms of a redox-active solid thin film, successfully applying redox polymer theory to model how charge transport is affected by redox dopant loading. To investigate local structural changes at interfaces, this dissertation explores the incorporation of surface-enhanced Raman spectroscopy (SERS) to electroanalytical experiments. I demonstrate the viability of scanning electrochemical microscopy (SECM) to control local surface pH at a self-assembled monolayer and SERS to track the resulting structures. To broaden the application of electrochemical SERS to carbon-based electrodes, I demonstrate a hybrid nanoparticle-graphene substrate and use it to characterize the electrochemical reduction of anthraquinone-2,6-disulfonate on graphene. Further, I show the capability of SECM to induce SERS-detectable changes at these carbon substrates and suggest further possible research directions for this and other projects using coupled Raman-SECM. Overall, this work demonstrates several new methods for deeper fundamental understanding of complex electrode interfaces, probing charge transport, local solution perturbation effects, and adsorption chemistry.
Graduation Semester
2022-05
Type of Resource
Thesis
Handle URL
https://hdl.handle.net/2142/115644
Copyright and License Information
Copyright 2022 Kendrich Hatfield

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Graduate Theses and Dissertations at Illinois