Date of Award

Fall 2023

Project Type

Dissertation

Program or Major

Chemistry

Degree Name

Doctor of Philosophy

First Advisor

Christine A Caputo

Second Advisor

Roy Planalp

Third Advisor

Anyin Li

Abstract

Solar fuel generation has garnered attention in recent years as a renewable source for syngas (hydrogen and carbon monoxide) evolution. Difficulty in designing one-pot systems that can generate tunable ratios of hydrogen and carbon monoxide gases has persisted. In this thesis, a photocatalytic system for the generation of syngas under simulated solar irradiance is described that satisfies these challenges using black phosphorus (BP) and carbon nitride loaded with Co2+ active sites (Co@C3N4) to form a heterojunction. This thesis will present the ability to tune the syngas ratio by controlling the %wt of BP in the heterojunction. The oxidative power of this heterojunction was also explored by employing non-sacrificial reagents, specifically 4-methylbenzyl alcohol and glucose, as oxidation substrates in an effort to generate value-added oxidized organic by-products. We present our preliminary findings that show overall low conversion of oxidation substrates as well as syngas ratios significantly higher than what was observed in previous experiments with a sacrificial reagent. Fundamental electron dynamics for both reductive and oxidative pathways, as determined using transient absorption spectroscopy, are also described herein. The implications of these electron transfer rates for tuning the activity of the heterojunction and to promote targeted and selective product generation are discussed. Finally, the development of C3N4 electrodes for use in electrocatalytic schemes is also described.

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