Defense Date

2020

Document Type

Dissertation

Degree Name

Doctor of Philosophy

Department

Chemical and Life Science Engineering

First Advisor

Dr. B. Frank Gupton

Second Advisor

Dr. Carlos E. Castano

Abstract

Herein, a wholistic analysis of the viability of monolithic catalysts for redox reactions is presented. The interdisciplinary approach taken in this systematic study included preparation and investigation on Pd-on-carbon monoliths as catalysts in a flow and electrochemical settings.

The Suzuki-Miyaura reaction-focused study led to rational design, preparation, and successful application of Pd0-on-graphene oxide (GO) monolithic catalysts in flow conditions. In this study a combination of chemical reduction, freeze-casting, and vapor-phase reduction processes was applied to Pd-GO structures leading to the preparation of these monoliths. The Suzuki flow synthesis reactions revealed that the monolithic structure led to significantly improved catalytic longevity compared to 2D solid-supported catalysts. Nonetheless, the turnover frequency and product metal contamination (leaching-off) analysis indicated superior performance for monolithic catalysts.

Electrochemical Wacker-type oxidations are among the most common reactions in the industry. However, in order to prepare a rationally designed monolithic catalyst for this reaction, further catalyst studies were required. Therefore, a comprehensive study on 2-dimensional Pd-on-graphene nanoplatelets was conducted, leading to a proposed industrial design space for oxidation catalyst manufacturing. Afterwards, as a proof of concept viability of PdII-on glassy carbon (GC) monoliths were used as catalytic electrodes for Wacker-type oxidation in the electrochemical setting.

Via this approach, a comprehensive investigation and validation of monolithic catalyst preparation and applications in industrially feasible synthetic processes, including catalytically different redox reactions in flow and electrochemical settings, were successfully attained.

Rights

© The Author

Is Part Of

VCU University Archives

Is Part Of

VCU Theses and Dissertations

Date of Submission

8-5-2020

Available for download on Thursday, August 05, 2021

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