Proton-coupled electron transfer in molecular and material catalysis

Proton-coupled electron transfer (PCET) plays an important role in a variety of electrochemical and photo-excited reactions occurring in molecular, material, and biological systems. In this thesis, the role of PCET in hydrogen evolution molecular electrocatalysts, and iron-doped nickel-oxyhydroxide thin films used for oxygen evolution reaction, are explored by means of quantum chemistry. Detailed electronic structural analysis performed using density functional theory is used to provide atomic level understanding of these catalytic systems. The electron-proton nonadiabaticity of PCET process is investigated for the phenoxyl/phenol self-exchange reaction, and the results show that the vibronic coupling is dependent on the molecular geometry. This diagnostic is important for the calculation of PCET rate constants. The rate constants and kinetic isotope effects for concerted PCET in a set of hydroquinone derivatives are calculated and analyzed in comparison with experimental data.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2019

Author dc:creator

• Karippara Harshan, Aparna

Contributors dc:contributor

• Hammes-Schiffer, Sharon
• Makri, Nancy
• Vura-Weis, Joshua
• Olshansky, Lisa

• Proton-coupled electron transfer
• PCET
• Molecular electrocatalysts
• Density Functional Theory
• Hydrogen Evolution Reaction
• Oxygen Evolution Reaction
• Vibronic coupling

Statement dc:rights

• Copyright 2018 Aparna Karippara Harshan

Language dc:language

en

Handle dc:identifier

http://hdl.handle.net/2142/102896

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/102896