Electrochemical and spectroelectrochemical investigations of interfacial electrode processes

Hatfield, Kendrich O'Donaghue

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

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

Copyright and License Information

Copyright 2022 Kendrich Hatfield

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