Solvent-free carbonate-promoted transformations for CO2 utilization
Abstract/Contents
- Abstract
- Utilization of captured greenhouse gas emissions for the synthesis of fuels and chemicals is one of many potential strategies to address the impacts of atmospheric greenhouse gas accumulation. In order for carbon capture and utilization to lower net emissions relative to conventional synthesis, the employed processes must account for several factors including minimization of the use of energy-intensive reagents. One promising general reaction scheme for carbon capture and utilization involves the use of carbon dioxide (CO2) for the synthesis of carboxylic acids, which are a diverse class of chemicals with many uses. Conventional carboxylation reactions involve the consumption of energy-intensive resources, however, and are thus not well suited as a strategy for emissions mitigation. To address this, prior work has demonstrated the use of carbonate salts in solvent-free reaction media to promote carboxylation reactions for CO2 utilization. Carbonates are abundant and regenerable reagents, but in conventional (solution-phase) organic reaction media are only weakly basic and therefore incapable of performing the necessary deprotonation step of the carboxylation reaction mechanism for most substrates of interest. Solvent-free carbonate-promoted reactions overcome this limitation for some substrates, but a better understanding of the physical properties of carbonate salts in solvent-free reaction media was required in order to apply this chemistry more generally. The work described in this dissertation involves investigation of the physical properties which enable reactions of carbonate salts with solid- and gas-phase substrates under solvent-free reaction conditions. For carboxylation of solid substrates, carbonate reactivity was found to rely on the formation of molten eutectic mixtures at intermediate temperatures. To extend the scope of carbonate reactivity beyond eutectic-forming systems and provide access to gas-phase substrates, dispersion of carbonate salts onto high surface area materials was investigated. Surface dispersion was found to result in the formation of a structurally disordered and mobile carbonate species with enhanced basicity relative to the bulk crystalline species. The improved understanding of carbonate reactivity that was obtained through these studies was used to investigate and improve upon various reactions of interest for CO2 utilization, including the formation of a monomer for polyester production from a waste biomass-derived substrate and a catalytic CO2 hydrogenation reaction that could be used to provide the feedstock for biological production of liquid fuels
Description
| Type of resource | text |
|---|---|
| Form | electronic resource; remote; computer; online resource |
| Extent | 1 online resource |
| Place | California |
| Place | [Stanford, California] |
| Publisher | [Stanford University] |
| Copyright date | 2021; ©2021 |
| Publication date | 2021; 2021 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Author | Frankhouser, Amy Delano |
|---|---|
| Degree supervisor | Kanan, Matthew William, 1978- |
| Thesis advisor | Kanan, Matthew William, 1978- |
| Thesis advisor | Karunadasa, Hemamala |
| Thesis advisor | Waymouth, Robert M |
| Degree committee member | Karunadasa, Hemamala |
| Degree committee member | Waymouth, Robert M |
| Associated with | Stanford University, Department of Chemistry |
Subjects
| Genre | Theses |
|---|---|
| Genre | Text |
Bibliographic information
| Statement of responsibility | Amy Frankhouser |
|---|---|
| Note | Submitted to the Department of Chemistry |
| Thesis | Thesis Ph.D. Stanford University 2021 |
| Location | https://purl.stanford.edu/kv943wz4517 |
Access conditions
- Copyright
- © 2021 by Amy Delano Frankhouser
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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