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Photoinduced Electron Transfer at Dye-Sensitized Oxide Interfaces
Photoinduced Electron Transfer at Dye-Sensitized Oxide Interfaces
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211152038
- ISBN
- 9798383691632
- DDC
- 540
- 서명/저자
- Photoinduced Electron Transfer at Dye-Sensitized Oxide Interfaces
- 발행사항
- [Sl] : The University of North Carolina at Chapel Hill, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 405 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-02, Section: B.
- 주기사항
- Advisor: Meyer, Gerald J.
- 학위논문주기
- Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2024.
- 초록/해제
- 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.
- 일반주제명
- Chemistry
- 일반주제명
- Inorganic chemistry
- 일반주제명
- Physical chemistry
- 일반주제명
- Nanotechnology
- 키워드
- Marcus theory
- 키워드
- Solar energy
- 기타저자
- The University of North Carolina at Chapel Hill Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-02B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
008250123s2024 us c eng d■001000017162661
■00520250211152038
■006m o d
■007cr#unu||||||||
■020 ▼a9798383691632
■035 ▼a(MiAaPQ)AAI31336042
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a540
■1001 ▼aLoague, Quentin R.
■24510▼aPhotoinduced Electron Transfer at Dye-Sensitized Oxide Interfaces
■260 ▼a[Sl]▼bThe University of North Carolina at Chapel Hill▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a405 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-02, Section: B.
■500 ▼aAdvisor: Meyer, Gerald J.
■5021 ▼aThesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2024.
■520 ▼aThe 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.
■590 ▼aSchool code: 0153.
■650 4▼aChemistry
■650 4▼aInorganic chemistry
■650 4▼aPhysical chemistry
■650 4▼aNanotechnology
■653 ▼aDye-sensitized solar cells
■653 ▼aGerischer diagrams
■653 ▼aInterfacial electron transfer
■653 ▼aMarcus theory
■653 ▼aSolar energy
■690 ▼a0485
■690 ▼a0488
■690 ▼a0494
■690 ▼a0652
■71020▼aThe University of North Carolina at Chapel Hill▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-02B.
■790 ▼a0153
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17162661▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
