Abstract

The presented dissertation focuses on the design, synthesis, and characterization of metal-organic frameworks (MOFs) composed of earth-abundant elements the exhibit photoredox activity and studied their application as heterogeneous photocatalysts in organic synthesis and in solar-to-chemical energy conversion. In particular, the structure-property relationships of titanium-based MOFs relating the structure of the organic building unit and the photophysical and photochemical activity of the solid material is studied. The first novel family of seven MOFs isoreticular to MIL-125-NH2, includes functionalized with N-alkyl groups with increasing chain length (methyl to heptyl) and with varying connectivity (primary or secondary). The functionalized materials displayed reduced optical bandgaps correlated with the increased inductive donor ability of the alkyl substituents, enhanced excited-state lifetimes, mechanistic information towards visible light CO2 reduction, and improved water stability. The second family of titanium MOFs was prepared with a new secondary building unit and organic links of varying lengths, for which Their crystal structure was solved utilizing powder X-ray diffraction crystallography. This work provides guidelines for the next generation of photocatalyst for the conversion of solar-to-chemical energy and other organic transformations.

Graduation Date

2018

Semester

Summer

Advisor

Uribe Romo, Fernando

Degree

Doctor of Philosophy (Ph.D.)

College

College of Sciences

Department

Chemistry

Degree Program

Chemistry

Format

application/pdf

Identifier

CFE0007153

URL

http://purl.fcla.edu/fcla/etd/CFE0007219

Language

English

Release Date

August 2018

Length of Campus-only Access

None

Access Status

Doctoral Dissertation (Open Access)

Included in

Chemistry Commons

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