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Synthesis and study of perylene-bridge-anchor derivatives for metal oxides semiconductor sensitization
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TitleInfo
Title
Synthesis and study of perylene-bridge-anchor derivatives for metal oxides semiconductor sensitization
Name
(type = personal)
NamePart
(type = family)
Fan
NamePart
(type = given)
Hao
NamePart
(type = date)
1991-
DisplayForm
Hao Fan
Role
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(authority = RULIB)
author
Name
(type = personal)
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(type = family)
Galoppini
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Elena
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Elena Galoppini
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Advisory Committee
Role
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(authority = RULIB)
chair
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(type = personal)
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(type = family)
Lockard
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(type = given)
Jenny
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Jenny Lockard
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Advisory Committee
Role
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(authority = RULIB)
internal member
Name
(type = personal)
NamePart
(type = family)
Szostak
NamePart
(type = given)
Michal
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Michal Szostak
Affiliation
Advisory Committee
Role
RoleTerm
(authority = RULIB)
internal member
Name
(type = personal)
NamePart
(type = family)
Teplyakov
NamePart
(type = given)
Andrew V.
DisplayForm
Andrew V. Teplyakov
Affiliation
Advisory Committee
Role
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(authority = RULIB)
outside member
Name
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NamePart
Rutgers University
Role
RoleTerm
(authority = RULIB)
degree grantor
Name
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NamePart
Graduate School - Newark
Role
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school
TypeOfResource
Text
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theses
OriginInfo
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2018
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2018-10
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2018
Language
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eng
Abstract
(type = abstract)
Electron transfer at the interface between a photoactive molecule and large-bandgap nanostructured metal oxide (MOn) semiconductors remains at the center of intense research in numerous areas for solar energy conversion. Organic chromophore-bridge-anchor compounds are important to the studies of heterogeneous charge transfer on MOn semiconductors and are widely employed in various photochemistry researches. In this thesis, we report the synthesis of 2,5-di-tert-butylperylene (DTBuPe) and a series of DTBuPe-bridge-anchor compounds, and study their steady state photochemical properties in solutions as well as on nanostructured metal oxide semiconductor films.
The thesis described a practical pathway to synthesize the DTBuPe, and further modification of the DTBuPe framework. Two modification routes were employed; one starting from formylation, which can be followed by reduction, oxidation or other functional group transformation of the aldehyde group. The second route starts from bromination of the framework, followed by various palladium catalyzed cross-coupling reactions. Through these methods, a series of DTBuPe-bridge-anchor derivatives were synthesized.
The spectroscopic properties of DTBuPe-bridge-anchor derivatives in solution and bound to nanostructured semiconductor surfaces were also investigated by absorption and emission spectra. 8,11-di-tert-Butylperylene-3-carboxylic acid (DTBuPe-COOH), 3-(8,11-di-tert-Butylperylen-3-yl)propanoic acid (DTBuPe-Prop-COOH), 4-(8,11-di-tert-Butylperylen-3-yl)benzoic acid (DTBuPe-Ph-COOH) and perylene-3-carboxylic acid (Pe-COOH) were bound to both TiO2 and ZrO2 films and characterized by absorption and emission spectra. A comparison of the properties of DTBuPe-bridge-anchor/TiO2 and perylene/TiO2 is made, and the influence of t-butyl spacing group, as well as different bridge units, is investigated. In addition, perylene was functionalized with an azide group (9-(4-azidophenyl)-2,5-di-tert-Butylperylene (DTBuPe-Ph-N3)) for click chemistry. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction of DTBuPe-Ph-N3 was successfully performed in solution and on ZnO nanostructured surfaces which was functionalized with propiolic acid in a stepwise functionalization process. The sensitized ZnO surface was characterized by SEM, XPS and TA. The morphology of ZnO nanorod was preserved and strong electronic coupling between sensitizer and semiconductor film was obtained.
The thesis described a practical pathway to synthesize the DTBuPe, and further modification of the DTBuPe framework. Two modification routes were employed; one starting from formylation, which can be followed by reduction, oxidation or other functional group transformation of the aldehyde group. The second route starts from bromination of the framework, followed by various palladium catalyzed cross-coupling reactions. Through these methods, a series of DTBuPe-bridge-anchor derivatives were synthesized.
The spectroscopic properties of DTBuPe-bridge-anchor derivatives in solution and bound to nanostructured semiconductor surfaces were also investigated by absorption and emission spectra. 8,11-di-tert-Butylperylene-3-carboxylic acid (DTBuPe-COOH), 3-(8,11-di-tert-Butylperylen-3-yl)propanoic acid (DTBuPe-Prop-COOH), 4-(8,11-di-tert-Butylperylen-3-yl)benzoic acid (DTBuPe-Ph-COOH) and perylene-3-carboxylic acid (Pe-COOH) were bound to both TiO2 and ZrO2 films and characterized by absorption and emission spectra. A comparison of the properties of DTBuPe-bridge-anchor/TiO2 and perylene/TiO2 is made, and the influence of t-butyl spacing group, as well as different bridge units, is investigated. In addition, perylene was functionalized with an azide group (9-(4-azidophenyl)-2,5-di-tert-Butylperylene (DTBuPe-Ph-N3)) for click chemistry. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction of DTBuPe-Ph-N3 was successfully performed in solution and on ZnO nanostructured surfaces which was functionalized with propiolic acid in a stepwise functionalization process. The sensitized ZnO surface was characterized by SEM, XPS and TA. The morphology of ZnO nanorod was preserved and strong electronic coupling between sensitizer and semiconductor film was obtained.
Subject
(authority = RUETD)
Topic
Chemistry
Subject
(authority = ETD-LCSH)
Topic
Metallic oxides--Synthesis
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Rutgers University Electronic Theses and Dissertations
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ETD_9096
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electronic resource
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application/pdf
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Extent
1 online resource (143 pages) : illustrations
Note
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Ph.D.
Note
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Includes bibliographical references
Note
(type = statement of responsibility)
by Hao Fan
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Title
Graduate School - Newark Electronic Theses and Dissertations
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rucore10002600001
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Identifier
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doi:10.7282/t3-nzt8-z775
Genre
(authority = ExL-Esploro)
ETD doctoral
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Rights
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The author owns the copyright to this work.
RightsHolder
(type = personal)
Name
FamilyName
Fan
GivenName
Hao
Role
Copyright Holder
RightsEvent
Type
Permission or license
DateTime
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2018-07-05 15:23:16
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Name
Hao Fan
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Copyright holder
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Rutgers University. Graduate School - Newark
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Author Agreement License
Detail
I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
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Embargo
DateTime
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2018-10-31
DateTime
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2020-10-30
Detail
Access to this PDF has been restricted at the author's request. It will be publicly available after October 30th, 2020.
Copyright
Status
Copyright protected
Availability
Status
Open
Reason
Permission or license
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windows xp
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2018-08-02T16:13:44
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2018-08-02T16:13:44
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