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Reactivity of Transition Metal Hydride Complexes in Energy Conversion Processes
Reactivity of Transition Metal Hydride Complexes in Energy Conversion Processes
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20250211153040
- ISBN
- 9798346868125
- DDC
- 540
- 저자명
- Isaacs, Diane P.
- 서명/저자
- Reactivity of Transition Metal Hydride Complexes in Energy Conversion Processes
- 발행사항
- [Sl] : The University of North Carolina at Chapel Hill, 2024
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2024
- 형태사항
- 186 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 86-06, Section: B.
- 주기사항
- Advisor: Dempsey, Jillian L.
- 학위논문주기
- Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2024.
- 초록/해제
- 요약A majority of our energy (ca. 74%) comes from fossil fuels linked to harmful emissions of CO2. Many alternatives to fossil fuels, such as solar and wind, require the collection and storage of energy. However, the current energy storage infrastructure is not sufficient to store the energy for later use. A promising solution to the energy storage problem is to store the energy in chemical bonds as energy-dense gases or liquid fuels. Energy-dense fuels can be formed through CO2 reduction, N2 reduction, and H+ reduction reactions mediated by catalysts. Transition metal hydride complexes are key intermediates in many of these catalytic fuel forming reactions. They mediate the movement of protons and electrons to form energy-dense fuels. Often the movement of these protons and electrons is coupled in proton-coupled electron transfer (PCET) reactions. It is important to understand the PCET mechanisms for these transition metal hydride complexes as catalyst to determine ways to optimize conditions while minimizing harsh conditions.This work probes the reactivity of transition metal hydride complexes and interogates how they operate in order to develop design principles for efficient catalysts. First, the mechanism and reactivity for the light driven formation of a transition metal hydride complex was investigated through in situ photo 1H-NMR monitoring and quantum yields. Next, a series of tungsten hydride complexes and the putative intermediates formed by PCET reactivity were synthesized and characterized. This is followed by a preliminary investigation into the PCET mechanism of one of the tungsten hydride complexes using 2D exchange spectroscopy (EXSY) and stopped-flow rapid mixing techniques coupled with optical spectroscopy. Lastly, an iridium catalyst was investigated to determine its viability in the electrochemical Guerbet reaction by upgrading a lower chain alcohol to a higher chain alcohol avoiding the harsh conditions associated with the thermal Guerbet reaction.
- 일반주제명
- Chemistry
- 일반주제명
- Inorganic chemistry
- 일반주제명
- Physical chemistry
- 키워드
- Metal hydrides
- 키워드
- Chemical bonds
- 기타저자
- The University of North Carolina at Chapel Hill Chemistry
- 기본자료저록
- Dissertations Abstracts International. 86-06B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■020 ▼a9798346868125
■035 ▼a(MiAaPQ)AAI31638625
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a540
■1001 ▼aIsaacs, Diane P.
■24510▼aReactivity of Transition Metal Hydride Complexes in Energy Conversion Processes
■260 ▼a[Sl]▼bThe University of North Carolina at Chapel Hill▼c2024
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2024
■300 ▼a186 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 86-06, Section: B.
■500 ▼aAdvisor: Dempsey, Jillian L.
■5021 ▼aThesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2024.
■520 ▼aA majority of our energy (ca. 74%) comes from fossil fuels linked to harmful emissions of CO2. Many alternatives to fossil fuels, such as solar and wind, require the collection and storage of energy. However, the current energy storage infrastructure is not sufficient to store the energy for later use. A promising solution to the energy storage problem is to store the energy in chemical bonds as energy-dense gases or liquid fuels. Energy-dense fuels can be formed through CO2 reduction, N2 reduction, and H+ reduction reactions mediated by catalysts. Transition metal hydride complexes are key intermediates in many of these catalytic fuel forming reactions. They mediate the movement of protons and electrons to form energy-dense fuels. Often the movement of these protons and electrons is coupled in proton-coupled electron transfer (PCET) reactions. It is important to understand the PCET mechanisms for these transition metal hydride complexes as catalyst to determine ways to optimize conditions while minimizing harsh conditions.This work probes the reactivity of transition metal hydride complexes and interogates how they operate in order to develop design principles for efficient catalysts. First, the mechanism and reactivity for the light driven formation of a transition metal hydride complex was investigated through in situ photo 1H-NMR monitoring and quantum yields. Next, a series of tungsten hydride complexes and the putative intermediates formed by PCET reactivity were synthesized and characterized. This is followed by a preliminary investigation into the PCET mechanism of one of the tungsten hydride complexes using 2D exchange spectroscopy (EXSY) and stopped-flow rapid mixing techniques coupled with optical spectroscopy. Lastly, an iridium catalyst was investigated to determine its viability in the electrochemical Guerbet reaction by upgrading a lower chain alcohol to a higher chain alcohol avoiding the harsh conditions associated with the thermal Guerbet reaction.
■590 ▼aSchool code: 0153.
■650 4▼aChemistry
■650 4▼aInorganic chemistry
■650 4▼aPhysical chemistry
■653 ▼aMetal hydrides
■653 ▼aChemical bonds
■653 ▼aEnergy storage infrastructure
■653 ▼aOptical spectroscopy
■690 ▼a0485
■690 ▼a0488
■690 ▼a0494
■71020▼aThe University of North Carolina at Chapel Hill▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g86-06B.
■790 ▼a0153
■791 ▼aPh.D.
■792 ▼a2024
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17164748▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
