Computational study of ionic liquids/electrode interfacial reactions for environmental and energy applications
No Thumbnail Available
Authors
Meeting name
Sponsors
Date
Journal Title
Format
Thesis
Subject
Abstract
[EMBARGOED UNTIL 12/01/2025] Electrochemistry in Ionic Liquid (IL) electrolytes is an area of research with significant opportunity for innovation and of high relevance for environmental and energy applications. While computational chemistry methods exist and have continuously evolved over recent decades and contributed significantly to providing complementary information and insight for experimental physical science, there is relatively limited knowledge about applying them for electrochemical problems. This is due to the complication of the heterogeneous electrochemical interface and system. It is more challenging to apply computational methods to understand electrode/IL interface reactions and processes since ILs and/or IL containing electrolytes, owing to their unique nature of ions interacting with other ions, analytes, solvent molecules, and electrodes, add additional complexity to the current methods. This dissertation addresses important aspects of this challenge by taking three topics of electrochemistry with IL-based electrolytes and systematically leverages computational tools to advance the fundamental understanding of these IL based electrochemical systems. This approach leads to advancements of theoretical considerations regarding IL electrochemistry and to progress in the practical implementation of respective calculations. The first research subject is to understand the detail mechanisms of the dissociative reduction of trichloroethylene (TCE), which is important for TCE remediation. Computational approaches are proposed and used for the study of reaction pathways of TCE in an IL/acetonitrile mixed electrolyte. Systematic considerations of the thermodynamics, kinetics, and electrolyte structure related issues are included in the computational study. The second research subject is understanding the CO2 physical chemistry such as conductivity, mass density, and structure of the IL and their impact on CO2 solubility and adsorption that are valuable for the development of real time and continuous CO2 sensor applications. Computational methods are utilized to understand the mechanism that leads to selective impedance variation upon CO2 and methane exposure. The third research topic is dedicated to further computational methods for the study of CO2 and N2O reduction in IL electrolytes. Bulk, and surface structures of electrolyte, as well as the reaction pathways of CO2 and N2O reductions in these electrochemical systems are investigated, and novel methods to study gaseous molecules' redox chemistry in the IL electrolytes are developed, based on computational chemistry. With each of the model problems based on IL and/or IL containing electrolytes, calculation methods were proposed, implemented, and refined. The results of this work contribute to the advancement of computational chemistry to the complex field of IL and electrode interface electrochemistry, which offers solutions to critical environmental and energy related challenges.
Table of Contents
DOI
PubMed ID
Degree
Ph. D.