Development of electronic structure and kinetics methods for the rational design of electrocatalysts

Computational modeling has untapped potential for novel material and chemical discovery. In this thesis, we explore ways to improve existing modeling methods, and how to apply these methods to design novel graphite-conjugated catalysts (GCCs). For improving electronic structure methods, we first present an extended study of bootstrap embedding theory (BET) and its ability to recover static correlation, as well as a proof on BET's ideal convergence properties. We then present a theoretical analysis using density functional theory (DFT) on a class of GCCs containing cationic nitrogen atoms, which are particularly active for catalyzing the oxygen reduction reaction (ORR). Using a mixture of high-throughput screening, statistical analysis, and computational exploration guided by chemical intuition, we design several novel GCCs, several of which DFT predicts would have enhanced activity above existing GCCs. Furthermore, our analysis reveals that known ORR scaling relations hold for GCCs, but hint at the possibility of breaking these relations with careful molecular engineering of the GCC active sites.

Name thesis:degree_name

Doctoral

Department dc:contributor.department

Massachusetts Institute of Technology. Department of Chemistry

Grantor dc:publisher

Massachusetts Institute of Technology

Year dc:date.issued

2019

Author dc:creator

• Ricke, Nathan Darrell Peterson.

Advisor dc:contributor.advisor

• Troy Van Voorhis.

• Chemistry.

Statement dc:rights

• MIT theses are protected by copyright. They may be viewed, downloaded, or printed from this source but further reproduction or distribution in any format is prohibited without written permission.

Licence dc:rights.uri

• http://dspace.mit.edu/handle/1721.1/7582

Language dc:language.iso

eng

Handle dc:identifier.uri

https://hdl.handle.net/1721.1/124051

OAI identifier oai:identifier

oai:dspace.mit.edu:1721.1/124051