Effects of Electronegative Substituents on the Redox Properties of Iron-Salen Derivative Catalysts
Open Access
Author:
Perdue, Brandon
Area of Honors:
Chemical Engineering
Degree:
Bachelor of Science
Document Type:
Thesis
Thesis Supervisors:
Michael John Janik, Thesis Supervisor Darrell Velegol, Thesis Honors Advisor
Keywords:
electrocatalysis density functional theory
Abstract:
Molecular electrocatalyst performance can be tuned by subtle changes in the electronic structure about the metal active center in order to generate high activity for electrolysis applications. Electrocatalyst performance is highly pertinent for energy, health, and sustainable processes, and therefore rationale modification of supporting ligands can impact important applications. Herein, 12 iron-salen derivatives are examined to determine how the ligand substituents affect redox properties and overall catalyst effectiveness. Density functional theory (DFT) calculations are used to examine the molecular redox reaction energetics. The addition of nitro group ligand substitutions decreases the stabilization of the reduced species formed via an electron-proton transfer. The addition of electron withdrawing groups such as nitro functional groups at multiple ligand positions stabilizes delocalization of charge across the molecule upon reduction. Overall, the study of ligand substituents can greatly impact the field of electrochemical reaction mechanisms and the design of future catalysts.
