This dissertation investigates the use of organic and semiconductor nanomaterials as chromophores in solar fuels production and energy transfer-mediated [2+2] cycloadditions. A series of novel N-annulated perylene chromophore amphiphiles was synthesized via a modular synthesis. These perylene amphiphiles were found to self-assemble in aqueous solution, forming extended ribbon-like nanostructures that could form gels in the presence of cross-linking divalent salts. The assemblies exhibited weak electronic coupling, unlike similar previously studied molecules, likely due to an edge-to-face interaction between perylene units. The assemblies were used to photosensitize a CO2 reduction catalyst which photocatalyzed the reduction of CO2 to CO under aqueous conditions in the presence of light and a sacrificial hole quencher. Photosensitization of a similar catalyst with CuInS2@ZnS quantum dots (QDs) was also explored; specifically, potential binding interactions between the catalyst and QDs’ surface was investigated by 1H NMR and UV-vis spectroscopies as well as cyclic voltammetry and X-ray techniques. Finally, QDs were investigated as triplet sensitizers of a [2+2] cycloaddition between olefins and imines to form azetidines. Imine substrates were found to undergo unproductive isomerization even when sensitized by QDs with excited state energies below that of the imines due to non-vertical energy transfer. This thesis demonstrates the challenges and potential of designing both organic soft material and semiconductor nanomaterials for photocatalytic applications.

Creator

• Nagasing, Benjamin

DOI

• https://doi.org/10.21985/n2-7fnn-tr78

Subject

• Chemistry

Language

• en

Alternate Identifier

• etdadmin_upload_787179
• http://dissertations.umi.com/northwestern:15434

Keyword

• cycloaddition
• Nanomaterials
• self-assembly
• Quantum dots
• Solar fuels
• photocatalysis

Date created

• 2020-01-01

Resource type

• Dissertation

Rights statement

• In Copyright