Abstract:

As climate change continues to progress, sustainable strategies to mitigate the effects are increasingly relevant. Electrocatalysis is a promising route for the clean conversion of greenhouse gases into benign products or value-added chemicals. Molecular electrocatalysts in particular are of interest due to their potential for selective and efficient conversion of small molecules into valuable feedstocks. This dissertation describes the use and advancement of a well-known electrocatalyst, iron tetraphenylporphyrin (FeTPP), for the activation of nitrous oxide (N₂O) and carbon dioxide (CO₂). First, we describe the application of FeTPP for the reduction of N₂O to N₂. This process was highly selective and stable, and demonstrated how we can leverage molecular electrocatalysts to overcome the kinetic limitations of N₂O activation. Next, we explore the vast parameter space in the model electroreduction reaction of CO₂ to CO on FeTPP. By utilizing autonomous electrochemistry, a unique set of reaction conditions that gave rise to a nearly 60-fold increase in the observed rate of reduction compared to the standard conditions were identified. Lastly, we detail attempts to integrate CO₂ capture and conversion into a single process using a variety of known molecular CO₂ electrocatalysts. While the results saw mixed success, the study lays the foundation for translation of the principles of typical reduction of free CO₂ to reduction of sorbent-captured CO₂.