The chemistry of transition metal complexes related to solar energy storage : H₂ production and small molecule (CO₂ and HX; X = Cl, Br) chemistry.
Name
771922602-MIT.pdf
Description
Full printable version
Size
14.99 MB
Format
Adobe PDF
Checksum (MD5)
5375679df7b79880a53b16405d6be509
Author(s)
Lee, Changhoon, Ph. D. Massachusetts Institute of Technology
Advisor(s)
Daniel G. Nocera.
Date Issued
2011
Publisher
Massachusetts Institute of Technology
Abstract
The studies in this thesis have focused on the chemistry of transition metal complexes related to solar energy storage: electrochemical H₂ production, HX splitting and CO₂ activation mediated by transition metal complexes. Transition metal complexes, for example with macrocyclic ligands, can catalyze electrochemical proton reduction, a half reaction of water splitting to H₂/O₂ by electricity generated by sunlight. The strategy for designing efficient molecular catalysts were explored by introducing a Hangman scaffold into metallomacrocyles. The study exhibits synthesis and electrochemistry of metallomacrocyles, and an example of Hangman effect for electrochemical H2 production. Thermodynamically demanding HX splitting to H₂/X₂ by sunlight can be a promising method for solar energy storage. To date, most HX splitting chemistry was studied with metal complexes based on 2"d or 3 rd row transition metals. Hence, the usage of cheaper first row metals is an imperative to discover economically viable catalytic systems. HX chemistry of Ni complexes and photoelimination of H₂ from Ni hydride complexes, and photoactivation of Ni-Cl bonds were studied. CO₂ can be utilized as a carrier of H₂ by the syntheses of liquid fuels from CO₂ and H₂. The challenge of using CO₂ as a precursor for organic molecules is the activation of strong O=CO bonds. The reaction with metal complexes is one of the methods to break or weaken the bonds. The CO₂ chemistry of Ni complexes was explored, and generation of a new binding mode of CO₂ and activation of CO₂ to CO were studied.
Description
Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2011.
Cataloged from PDF version of thesis.
Includes bibliographical references.
Subjects
Chemistry.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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