자료유형  

 학위논문

Control Number  

0017162661

International Standard Book Number  

9798383691632

Dewey Decimal Classification Number  

540

Main Entry-Personal Name  

Loague, Quentin R.

Publication, Distribution, etc. (Imprint  

[S.l.] : The University of North Carolina at Chapel Hill., 2024

Publication, Distribution, etc. (Imprint  

Ann Arbor : ProQuest Dissertations & Theses, 2024

Physical Description  

405 p.

General Note  

Source: Dissertations Abstracts International, Volume: 86-02, Section: B.

General Note  

Advisor: Meyer, Gerald J.

Dissertation Note  

Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2024.

Summary, Etc.  

요약The prevalent availability of sunlight positions solar energy as a sustainable alternative to carbon-based fuels. However, broad adoption hinges on effective solar energy capture and storage solutions. One approach involves converting solar energy and readily available chemical feedstocks, such as carbon dioxide and water, into liquid fuels using dye-sensitized photoelectrosynthesis cells (DSPECs). This dissertation provides insights into fundamental lateral and interfacial electron transfer reactions, central to DSPEC optimization. CHAPTER 1 details the electron transfer reactions that can be photoinitiated at semiconducting and conductive oxide interfaces sensitized to visible light with transition metal complexes, along with the experimental techniques and theories necessary to characterize these reactions. CHAPTER 2 explores interfacial electron transfer reactions of photocatalysts at sensitized transparent conductive oxides (TCOs). Marcus-Gerischer kinetic analysis quantified the reorganization energy, λ, which increased from 0.30 to 0.56 eV when electron-donating groups were replaced with electron withdrawing groups. CHAPTER 3 investigates interfacial and lateral self-exchange electron transfer reactions for molecular sensitizers: cis-[Ru(LL)(dcb)(NCS)2], where dcb is 4,4'-(CO2H)2-2,2'-bipyridine, and LL is dcb or another ligand. Marcus-Gerischer kinetic experiments revealed a reorganization energy, λ, smaller than predicted by dielectric continuum theory, suggesting electron transfer occurs directly to the Ru acceptor, contrary to previous literature.CHAPTER 4 and CHAPTER 5 explore the use of conjugated p-phenylene ethynylene bridge units to structurally gate vectorial electron transfer for Ru polypyridyl complexes: [Ru(bpy)2(LL)](PF6)2, where LL is a 4- substituted 2,2-bipyridine ligand bridged to an isophthalic group with a varying number of p-phenylene ethynylene units. Light absorption "opens" the gate by planarizing the p-phenylene ethynylene units, providing a conjugated pathway for electron transfer. After interfacial electron injection into the TCO, free rotation is restored, "closing" the gate and inhibiting recombination. Comparative studies with ionic bridged sensitizers revealed enhanced vectoral electron transfer was due to a smaller reorganization energy, not enhanced electronic coupling.CHAPTER 6 offers an overview of transient absorption spectroscopy (TA) as a kinetic tool for evaluating light-initiated chemical transformations. It includes an introduction to TA methods including complementary spectroscopic and electrochemical techniques. Lastly, CHAPTER 7 provides the details of an automated solar fuels product analysis system.

Subject Added Entry-Topical Term  

Chemistry.

Subject Added Entry-Topical Term  

Inorganic chemistry.

Subject Added Entry-Topical Term  

Physical chemistry.

Subject Added Entry-Topical Term  

Nanotechnology.

Index Term-Uncontrolled  

Dye-sensitized solar cells

Index Term-Uncontrolled  

Gerischer diagrams

Index Term-Uncontrolled  

Interfacial electron transfer

Index Term-Uncontrolled  

Marcus theory

Index Term-Uncontrolled  

Solar energy

Added Entry-Corporate Name  

The University of North Carolina at Chapel Hill Chemistry

Host Item Entry  

Dissertations Abstracts International. 86-02B.

Electronic Location and Access  

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Control Number  

joongbu:656514