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Interfacial Electron Transfer for So...

Bangle, Rachel E.

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Interfacial Electron Transfer for Solar Energy Conversion: Kinetic and Mechanistic Insights.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Interfacial Electron Transfer for Solar Energy Conversion: Kinetic and Mechanistic Insights./
Author:	Bangle, Rachel E.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2021,
Description:	302 p.
Notes:	Source: Dissertations Abstracts International, Volume: 82-12, Section: B.
Contained By:	Dissertations Abstracts International82-12B.
Subject:	Chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28418983
ISBN:	9798516057496

Interfacial Electron Transfer for Solar Energy Conversion: Kinetic and Mechanistic Insights.
Bangle, Rachel E.

Interfacial Electron Transfer for Solar Energy Conversion: Kinetic and Mechanistic Insights. - Ann Arbor : ProQuest Dissertations & Theses, 2021 - 302 p.

Source: Dissertations Abstracts International, Volume: 82-12, Section: B.

Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2021.

This item must not be sold to any third party vendors.

The ubiquity of sunlight makes solar energy a promising alternative to carbon fuels, but wide-spread applications will require solar energy storage. To this end, solar energy and earth-abundant chemical feedstocks might be converted to liquid fuels in devices termed dye-sensitized photoelectrosynthesis cells (DSPECs). This Dissertation seeks to build fundamental understandings of interfacial electron transfer (IET) reactions between molecular sensitizers and metal oxide (MOx) nanocrystals important to DSPEC optimization. Chapter 1 outlines the chemical processes involved in DSPEC operation and the semi-classical theories which describe IET.Chapters 2 develops a novel method to sensitize MOx materials through diazonium electrografting. Diazonium-substituting Ru-bis-terpyridine sensitizers were successfully anchored to MOx surfaces through alkaline-stable, covalent bonds. Though diazonium-electrografted photoelectrodes produced small photocurrents relative to traditional anchoring groups in acidic conditions, they achieved sustained photocurrents at pH 12.In Chapter 3, the IET mechanisms of dye-sensitized MOx core|shell materials generated through atomic layer deposition are discussed. Structural and kinetic analysis of Ru-polypyridyl-sensitized ZrO2|TiO2 and SnO2|TiO2 materials demonstrated that the rate and mechanism of IET could be controlled by the shell thickness and morphology.Chapters 4-7 explore IET reactions in dye-sensitized transparent conducting oxides (TCOs), which exhibit metallic behavior. In Chapter 4, a TCO displayed both anodic and cathodic capabilities, as the direction of photo-initiated IET with Ru-polypyridyl or Ru-bipyrazine sensitizers was controlled by applied potentials and sensitizer excited state localization. In Chapters 5-7, Marcus-Gerischer kinetic analysis allowed quantification of IET reorganization energies (λ). This showed that for a Ru water oxidation catalyst, proton-coupled IET exhibited a 0.4 eV larger λ than did electron transfer alone (Chapter 5). Marcus-Gerischer analysis also showed λ to increase systematically with IET distance for Ru-polypyridal and tri-aryl amine complexes located at defined positions within the TCO electric double layer (EDL) by layered ionic bridges (Chapter 6). In fact, within the outer-Helmholtz plane, IET was nearly activationless (λ ≈ 0.1 eV). This was attributed to electric fields in the EDL which drastically decreased the dielectric response of the polar solvents. Further, insensitivity to solvent dynamics between water, acetonitrile, methanol, and benzonitrile indicated IET was non-adiabatic, even at the smallest distances (Chapter 7).

ISBN: 9798516057496Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

Dye-sensitized Photoelectrosynthesis Cells

Interfacial Electron Transfer for Solar Energy Conversion: Kinetic and Mechanistic Insights.
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245 1 0 $a Interfacial Electron Transfer for Solar Energy Conversion: Kinetic and Mechanistic Insights.
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300 $a 302 p.
500 $a Source: Dissertations Abstracts International, Volume: 82-12, Section: B.
500 $a Advisor: Meyer, Gerald J.
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506 $a This item must not be sold to any third party vendors.
520 $a The ubiquity of sunlight makes solar energy a promising alternative to carbon fuels, but wide-spread applications will require solar energy storage. To this end, solar energy and earth-abundant chemical feedstocks might be converted to liquid fuels in devices termed dye-sensitized photoelectrosynthesis cells (DSPECs). This Dissertation seeks to build fundamental understandings of interfacial electron transfer (IET) reactions between molecular sensitizers and metal oxide (MOx) nanocrystals important to DSPEC optimization. Chapter 1 outlines the chemical processes involved in DSPEC operation and the semi-classical theories which describe IET.Chapters 2 develops a novel method to sensitize MOx materials through diazonium electrografting. Diazonium-substituting Ru-bis-terpyridine sensitizers were successfully anchored to MOx surfaces through alkaline-stable, covalent bonds. Though diazonium-electrografted photoelectrodes produced small photocurrents relative to traditional anchoring groups in acidic conditions, they achieved sustained photocurrents at pH 12.In Chapter 3, the IET mechanisms of dye-sensitized MOx core|shell materials generated through atomic layer deposition are discussed. Structural and kinetic analysis of Ru-polypyridyl-sensitized ZrO2|TiO2 and SnO2|TiO2 materials demonstrated that the rate and mechanism of IET could be controlled by the shell thickness and morphology.Chapters 4-7 explore IET reactions in dye-sensitized transparent conducting oxides (TCOs), which exhibit metallic behavior. In Chapter 4, a TCO displayed both anodic and cathodic capabilities, as the direction of photo-initiated IET with Ru-polypyridyl or Ru-bipyrazine sensitizers was controlled by applied potentials and sensitizer excited state localization. In Chapters 5-7, Marcus-Gerischer kinetic analysis allowed quantification of IET reorganization energies (λ). This showed that for a Ru water oxidation catalyst, proton-coupled IET exhibited a 0.4 eV larger λ than did electron transfer alone (Chapter 5). Marcus-Gerischer analysis also showed λ to increase systematically with IET distance for Ru-polypyridal and tri-aryl amine complexes located at defined positions within the TCO electric double layer (EDL) by layered ionic bridges (Chapter 6). In fact, within the outer-Helmholtz plane, IET was nearly activationless (λ ≈ 0.1 eV). This was attributed to electric fields in the EDL which drastically decreased the dielectric response of the polar solvents. Further, insensitivity to solvent dynamics between water, acetonitrile, methanol, and benzonitrile indicated IET was non-adiabatic, even at the smallest distances (Chapter 7).
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650 4 $a Materials science. $3 543314
650 4 $a Alternative energy. $3 3436775
653 $a Dye-sensitized Photoelectrosynthesis Cells
653 $a Solar cells
653 $a Electron transfer theory
653 $a Solar fuels
653 $a Transparent Conducting Oxides
653 $a Interfacial Electron Transfer
653 $a Kinetics
653 $a Solar energy conversion
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710 2 $a The University of North Carolina at Chapel Hill. $b Chemistry. $3 1021872
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