| dc.description.abstract | This work focuses on forming carbon-carbon bonds between \CO and organic substrates utilizing electrochemistry alongside \CO eXpanded Electrolytes (CXEs) to enhance traditional synthesis techniques. Traditionally, electrochemical carboxylation reactions are plagued with low rates and selectivity due to the lack of \CO in the liquid phase resulting in the formation of pinacols and alcohols. Additionally, the effect of \CO concentration on the reaction rate can not be studied in traditional systems due to the low concentrations of \CO. Using CXEs, our electrochemistry was able to overcome the \CO availability limitations and find that the selectivity of the acetophenone carboxylation toward atrolactic acid is highly dependent on the concentration of \CO in the liquid phase. As the \CO concentration increased, the selectivity shifted from producing 1-phenylethanol ([\CO] 1.7 M). The electrochemical reduction of acetophenone was further studied using multiphysics simulations to provide insights into the kinetics of the acetophenone carboxylation. Typically, kinetic information on irreversible systems is not easily attainable through traditional electrochemical techniques Simulations were developed to regress key kinetic parameters characteristic of the acetophenone reduction and helped identify that the electrochemical chemical, electrochemical reaction pathway is the most likely reaction pathway. Additionally, we identified the first electron transfer as the rate-determining step. These simulations provide insight into fundamental electrochemistry previously unavailable for acetophenone reduction. The knowledge of the acetophenone system was extended to a study of a structure-property relationship specifically, the electron donating and withdrawing effects by adding and removing substituents. We found that adding a trifluoromethyl group to acetophenone shifted the reduction potential to less negative potentials decreasing the energy input required to reduce the molecule. Using styrene as a case study, we found that not having an electron-withdrawing group shifted the reduction potential more negative, increasing the energy required to reduce the molecule. Understanding the complex interaction between the electronic effects and electrochemistry can inform the types of chemistry that are available to undergo electrochemical carboxylation. In addition to the main body of work, several secondary projects were conducted. The first is developing a machine-learning model for extracting textual information from the literature. Roughly two-thirds of our time as researchers is spent on literature search and reading. Unfortunately, some of that time is wasted searching for relevant papers. Creating a searchable-subject material based database can free up a significant portion of a researcher's time. Our machine-learning model can annotate \CORR literature highlighting the critical parameters for electrochemical \CO reduction. This model was trained and tested on a dataset of 500 papers relating to \CO reduction. The result was a reasonably accurate model capable of tagging the features we wanted to be tagged. However, extraction and word vectoring are still in development to obtain the essential information. Another secondary project was developing high-surface area gold electrodes. The aim of this project was to push the gold-CXE system that was previously studied to the limit using high surface area gold. To further enhance the system, larger electrodes were required to increase the rate of CO formation. We developed a method to electroplate gold onto nickel foams. This resulted in a high surface area gold-plated electrode with a unique surface structure. In addition to plating the gold, we also investigated how the nickel surface effected the deposition of the gold. Etching the surface reduced the roughness of the surface, producing a more uniform coating. Both the dendritic and uniform gold electrocatalysts offer significant enhancements to electrochemically active surface area enhancements over traditional planar electrodes, potentially providing a scaleable route to electrochemically generated CO. Finally, the last project is Hypothesis-Based Career Planning. During this project, we developed a curriculum to help students better understand the roles available to them and lay the groundwork for their careers. Currently, many graduating students are unprepared to enter the workforce. Often, they lack the communication skills and network required to find a satisfactory position. The aim of this project is to supply students with a guide toward approaching career planning like research while developing their communication skills and building their networks. The students created and tested assumptions and hypotheses about potential career options so that they could be better informed about their decisions by conducting interviews with professional researchers. | |
