Date of Award

Spring 2026

Degree Type

Thesis

Department

Chemistry and Biochemistry

Director of Thesis

Aaron Vannucci

Second Reader

Sachini Dissanayake

Abstract

Copper catalysts play an important role in electrocatalytic oxidation reactions due to their redox flexibility and relative abundance compared to noble metal catalysts. In biological systems, copper metalloenzymes often achieve enhanced reactivity through an entatic state. Entasis is described as an active site or metal center being constrained to a geometric and electronic state, minimizing primary sphere reorganization energy and achieving higher rates of electron transfer.  This study investigates whether entasis can be achieved in synthetic molecular catalysts by immobilizing Cu(I) complexes onto metal oxide surfaces. Two Cu(I) complexes bearing carboxylate-functionalized ligands were examined both in homogeneous solution and when surface-bound to indium tin oxide (ITO) electrodes. Electrochemical characterization using cyclic voltammetry revealed that the homogeneous Cu(I) complexes displayed largely irreversible or quasi-reversible redox behavior, consistent with geometric distortion upon oxidation to Cu(II). In contrast, when immobilized on ITO electrodes, complexes rigidly bound to the ITO surface exhibited improved reversibility and smaller peak-to-peak separations, indicating that surface binding partially suppresses structural reorganization and achieves a higher energy state. By restricting the geometric distortion of the Cu(I)/Cu(II) redox couple, a higher energy, entatic state is induced.

The catalytic performance of the surface-bound Cu(I) species was evaluated through the electrochemical oxidation of benzyl alcohol using a nitroxyl radical mediator within a system analogous to the previous mechanism. Electrocatalytic studies are ongoing to optimize conditions. These findings highlight surface binding as a promising strategy for tuning the reactivity of copper molecular catalysts while maintaining accessible catalytic sites.

First Page

1

Last Page

37

Rights

© 2026, Rachel Kiser

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