First principles approaches towards modeling the electrochemical interface
Abstract/Contents
- Abstract
- In light of recent global climate trends resulting primarily from anthropogenic carbon emissions, there is a growing need to transition away from our reliance on fossil fuels. Perhaps the most promising approach towards this goal is the incorporation of renewable energy resources, such as wind and solar, more heavily into our energy grid. Unfortunately, these resources are inherently intermittent in time. To eliminate fossil fuels from our energy mix, grid-scale energy storage on both the daily and seasonal time scales will therefore be necessary. Energy storage on such an immense scale can in principle be practically achieved by storing energy in the form of chemical bonds; however, in practice the efficient conversion of low energy to high energy compounds (and vice-versa) is hampered by poor catalysts, despite decades of research efforts. This thesis focuses on developments in utilizing computer simulations to search for catalyst materials that are capable of efficiently electrochemically converting chemicals for energy storage. Density functional theory (DFT) has proven to be a very useful tool in simulating catalytic processes, and has successfully led to design tools for catalyst prediction. However, the application of DFT to electrochemical reactions has long been complicated by the complexity of the electrochemical interface: rather than simulating a gas-solid interface, we must simulate an electrified liquid-solid interface. In the first part of this thesis, we examine a commonly used and criticized approximation in our simulations, namely that electron transfer from a metal surface to an adsorbing molecule occurs on a timescale much faster than the timescale of the molecular adsorption. We then turn our attention to the treatment of the solvent in our simulations of the electrochemical interface, beginning with an explicit treatment where solvent molecules are explicitly included in the simulation. Finally, we explore an implicit treatment of the electrolyte by the incorporation of a polarizable dielectric continuum. We show that while implicit treatments offer a much simpler way to compute reaction energetics, great care must be taken both when considering parameterization of the model (for, among other things, solvation energies), and in understanding the electrostatics involved in the reaction events studied. We conclude by developing a new method for simulating electrochemical reaction events, by considering a hybrid explicit-implicit approach to modeling the interface. In particular, we show the surface charge to be a better descriptor for the driving force, as opposed to the traditionally considered work function of the electrode
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 | 2020; ©2020 |
| Publication date | 2020; 2020 |
| Issuance | monographic |
| Language | English |
Creators/Contributors
| Author | Gauthier, Joseph Allen |
|---|---|
| Degree supervisor | Jaramillo, Thomas Francisco |
| Degree supervisor | Noerskov, Jens |
| Thesis advisor | Jaramillo, Thomas Francisco |
| Thesis advisor | Noerskov, Jens |
| Thesis advisor | Qin, Jian, (Professor of Chemical Engineering) |
| Degree committee member | Qin, Jian, (Professor of Chemical Engineering) |
| Associated with | Stanford University, Department of Chemical Engineering. |
Subjects
| Genre | Theses |
|---|---|
| Genre | Text |
Bibliographic information
| Statement of responsibility | Joseph A. Gauthier |
|---|---|
| Note | Submitted to the Department of Chemical Engineering |
| Thesis | Thesis Ph.D. Stanford University 2020 |
| Location | electronic resource |
Access conditions
- Copyright
- © 2020 by Joseph Allen Gauthier
- License
- This work is licensed under a Creative Commons Attribution Non Commercial 3.0 Unported license (CC BY-NC).
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