Carbonate Chemistry and Carbon Dioxide Utilization: Electrochemical Synthesis of Dimethyl Carbonate and Metathesis Routes to Polycarbonates

Date of Award

Fall 1-1-2025

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Engineering and Applied Science

First Advisor

Anastas, Paul

Abstract

The transformation of carbon dioxide into commercially relevant chemicals and materials represents a critical pathway toward de-fossilization of the chemical industry. This dissertation presents pathways for converting CO2 into dimethyl carbonate, a versatile commodity chemical used as a precursor for polycarbonates. This work encompasses two main areas of original research: (1) electrochemical synthesis of dimethyl carbonate (DMC) using alternating polarity electrolysis in both semi-batch and CSTR-style flow systems, and (2) advanced olefin-metathesis polymerization strategies for producing polycarbonates from simple carbonate building blocks. The first section demonstrates palladium-catalyzed electrochemical conversion of CO2 and methanol to DMC under neat conditions using glassy carbon, eliminating the need for gold electrodes (Chapters 2 and 3). The initial study in semi-batch reactor examines the role of alternating polarity electrolysis to optimize product yields compared to static current conditions. The sequential chapter advances these findings by translating the optimized electrochemical conditions to a continuous stirred-tank reactor (CSTR)-like flow system, marking the first reported application of redox-neutral CO2-to-DMC chemistry in continuous flow. Uniquely, this work quantifies two other CO2RR products, methyl formate and formaldehyde, providing additional insights into product distributions and process efficiency. The second part, presented in Chapter 4, explores Ring-Opening Insertion Metathesis Polymerization (ROIMP) as a highly efficient route to polycarbonates from olefin-based carbonate. This ambient-condition polymerization technique achieves high monomer conversions within minimal reaction times, offering a complementary pathway to traditional carbonate metathesis methods without their equilibrium limitations. Future integration strategies are proposed to couple electrochemical DMC synthesis with established downstream polymerization processes, including carbonate metathesis and the application of ROIMP to CO2-derived monomers. Financing avenues for scaling sustainable innovations from laboratory to industrial implementation are discussed. This dissertation work aims to provide both practical advances in CO2 utilization chemistry and pathways toward sustainable polymer production that may contribute to the development of a circular carbon economy.

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